KR20230006570A - Novel Heteroaryl-Triazole Compounds as Agrochemicals - Google Patents

Abstract

The present invention relates to novel heteroaryl-triazole compounds of formula (I), in which the structural components X, R ¹ , R ² , R ³ and R ⁴ have the meanings given in the description, and formulations comprising such compounds and their use in the control of pests including arthropods and insects in the composition and plant protection, and their use for the control of ectoparasites in animals:
Formula (I)

Description

Novel Heteroaryl-Triazole Compounds as Agrochemicals

The present invention relates to novel heteroaryl-triazole compounds, preparations and compositions containing these compounds and their use in the control of pests, including arthropods and insects, in plant protection and their use for the control of ectoparasites in animals. will be.

Certain Heteroaryl-triazole compounds are described in WO 2017/192385 for use in controlling ectoparasites in animals, and in WO 2019/170626 and WO 2019/215198 in the control of pests, including arthropods and insects, in the field of plant protection. Use is disclosed. In addition, Patent Application Publication Nos. WO 2019/197468, WO 2019/201835, WO 2019/202077, WO 2019/206799, WO 2021/013719 and WO 2021/013720 in the field of control of ectoparasites in animals and plant protection in arthropods and Disclosed are certain heteroaryl-triazole compounds for use in controlling pests, including insects. WO 2020/002563, WO 2020/053364, WO 2020/053365, WO 2020/079198, WO 2020/094363, WO 2020/169445, WO 2020/182649, WO 2020/188014, WO 2020/188027 and WO 3027 Describes azole-amide compounds, all of which can be used as insecticides.

Modern plant protection products and veterinary ectoparasiticides must meet many demands, for example with respect to efficacy, persistence, spectrum and resistance-destroying properties. Problems of toxicity, compatibility with other active compounds or formulation auxiliaries play an important role together with the cost of synthesizing active compounds. Furthermore, tolerance may develop. For all these reasons, the search for new crop protection compositions or veterinary ectoparasiticides cannot be considered complete, and there is a constant need for new compounds with improved properties, at least in individual respects, compared to known compounds. do.

It was an object of the present invention to provide compounds broadening the spectrum of agrochemicals in various respects.

Therefore, the present invention provides compounds of formula (I):

In equation (construct 1-1):

X is O or S;

R ¹ is hydrogen;

R ² is selected from substructures Q1 and Q2 below, wherein the bond with the C=X-group is indicated by #;

In the above formula,

R ²¹ is halogen, -CN, -SF ₅ , C ₁ -C ₃ haloalkyl, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ haloalkylthio, C ₁ -C ₃ haloalkylsulfinyl, C ₁ - C ₃ haloalkylsulfonyl, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylsulfinyl, C ₁ -C ₃ alkylsulfonyl, C ₃ -C ₄ cycloalkylthio, C ₃ -C ₄ cycloalkyl group phenyl, C ₃ -C ₄ cycloalkylsulfonyl, phenylsulfonyl, wherein phenyl is substituted with 1 to 2 substituent(s) selected from the group of halogen, -CN, methyl, trifluoromethyl or trifluoromethoxy. optionally substituted); or cyclopropyl, wherein cyclopropyl is optionally substituted with 1 to 2 substituent(s) selected from the group of halogen, -CN, methyl or trifluoromethyl;

R ²² is hydrogen, halogen, -CN, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ haloalkoxy or C ₁ -C ₃ haloalkylsulfonyl;

R ³ is -CN or a substituent selected from substructure S1 below, wherein the bond to the pyrimidine is indicated by #;

in the expression,

R ³¹ is hydrogen or C ₁ -C ₃ alkyl;

R ³² is hydrogen, C ₃ -C ₆ cycloalkyl or C ₁ -C ₃ alkyl (C ₃ -C ₆ cycloalkyl and C ₁ -C ₃ alkyl are 1 to 2 selected from the group of halogen, -CN, C ₃ -C ₆ cycloalkyl and C ₁ -C ₃ alkoxy optionally substituted with two substituents);

R ⁴ is hydrogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or C ₃ -C ₄ cycloalkyl.

Compounds of formula (I) encompass any similarly existing diastereomers or enantiomers and E/Z isomers, as well as salts and N-oxides of compounds of formula (I), and their use for pest control. do.

Preferred radical definitions for the formulas specified above and below are provided below.

The present invention further provides compounds of formula (I):

In equation (construct 1-2):

X is O or S;

R ¹ is hydrogen;

R ² is selected from the substructures Q1 and Q2 below, wherein the bond with the C=X-group is indicated by #:

in the expression,

R ²¹ is halogen, -CN, -SF ₅ , C ₁ -C ₃ haloalkyl, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ haloalkylthio, C ₁ -C ₃ haloalkylsulfinyl, C ₁ - C ₃ haloalkylsulfonyl, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylsulfinyl, C ₁ -C ₃ alkylsulfonyl, C ₃ -C ₄ cycloalkylthio, C ₃ -C ₄ cycloalkyl group phenyl, C ₃ -C ₄ cycloalkylsulfonyl, phenylsulfonyl, wherein phenyl is substituted with 1 to 2 substituent(s) selected from the group of halogen, -CN, methyl, trifluoromethyl or trifluoromethoxy. optionally substituted); or cyclopropyl, wherein cyclopropyl is optionally substituted with 1 to 2 substituent(s) selected from the group of halogen, -CN, methyl or trifluoromethyl;

R ²² is hydrogen, halogen, -CN, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ haloalkoxy or C ₁ -C ₃ haloalkylsulfonyl;

R ³ is -CN or a substituent selected from substructure S1 below, wherein the bond to the pyrimidine is indicated by #:

in the expression,

R ³¹ is hydrogen or C ₁ -C ₃ alkyl;

R ³² is hydrogen, C ₃ -C ₆ cycloalkyl or C ₁ -C ₃ alkyl, wherein C ₃ -C ₆ cycloalkyl and C ₁ -C ₃ alkyl are halogen, -CN, C ₃ -C ₆ cycloalkyl and C ₁ -C ₃ alkoxy. to 3 substituents);

R ⁴ is hydrogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or C ₃ -C ₄ cycloalkyl.

Preferred (configuration 2-1) is a compound of formula (I), wherein

X is O or S;

R ¹ is hydrogen;

R ² is selected from the following substructures Q1 and Q2, wherein the bond with the C=X-group is indicated by #:

in the expression,

R ²¹ is fluorine, chlorine, bromine, iodine, -CN, cyclopropyl, 1-cyanocyclopropyl, 2,2-dichlorocyclopropyl, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethyl Toxy, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoro-2-iodoethoxy difluoromethylthio, trifluoromethylthio, 1,1, 2,2-tetrafluoroethylthio difluoromethylsulfonyl, trifluoromethylsulfonyl, 1,1,2,2-tetrafluoroethylsulfonyl, methylsulfonyl, ethylsulfonyl, cyclopropylsulfonyl or 4-chlorophenyl-sulfonyl;

R ²² is hydrogen, fluorine, chlorine, bromine, iodine, -CN, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl; ;

R ³ is -CN or a substituent selected from substructure S1 below, and the bond to the pyrimidine is indicated by #;

in the expression,

R ³¹ is hydrogen or methyl;

R ³² is hydrogen, cyclopropyl or C ₁ -C ₃ alkyl, wherein C ₁ -C ₃ alkyl is optionally substituted with 1 substituent selected from the group of halogen, -CN, cyclopropyl and methoxy;

R ⁴ is hydrogen, methyl or cyclopropyl.

Preferred (configuration 2-2) are also compounds of formula (I), wherein

X is O or S;

R ¹ is hydrogen;

R ² is selected from substructures Q1 and Q2 below, wherein the bond with the C=X-group is indicated by #;

in the expression,

R ²¹ is fluorine, chlorine, bromine, iodine, -CN, cyclopropyl, 1-cyanocyclopropyl, 2,2-dichlorocyclopropyl, difluoromethyl, 1,1-difluoroethyl, trifluoromethyl , chlorodifluoromethyl, 2-fluoropropan-2-yl, difluoromethoxy, trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetra Fluoro-2-iodoethoxy difluoromethylthio, trifluoromethylthio, 1,1,2,2-tetrafluoroethylthio, difluoromethylsulfonyl, trifluoromethylsulfonyl, 1 ,1,2,2-tetrafluoroethylsulfonyl, methylsulfanyl, methylsulfinyl, methylsulfonyl, ethylsulfonyl, cyclopropylsulfonyl or 4-chlorophenyl-sulfonyl;

R ²² is hydrogen, fluorine, chlorine, bromine, iodine, -CN, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl; ;

R ³ is -CN or a substituent selected from substructure S1 below, wherein the bond to the pyrimidine is indicated by #;

in the expression,

R ³¹ is hydrogen or methyl;

R ³² is hydrogen, cyclopropyl or C ₁ -C ₃ alkyl, wherein C ₁ -C ₃ alkyl is optionally substituted with 1 to 3 substituents selected from the group of fluorine, chlorine, -CN, cyclopropyl and methoxy is);

R ⁴ is hydrogen, methyl or cyclopropyl.

Further preferred (composition 3-1) are compounds of formula (I), wherein

X is O;

R ¹ is hydrogen;

R ² is (3,5-dibromophenyl), (3,5-dichlorophenyl), (3-chloro-5-methylsulfonylphenyl), (3-cyano-5-fluorophenyl), ( 3-fluorophenyl), (3-iodophenyl), 3-(1,1,2,2-tetrafluoroethylthio)phenyl, 3-(1-cyanocyclopropyl)-5-(trifluoro Lomethoxy)phenyl, 3-(difluoromethoxy)-5-fluorophenyl, 3-(difluoromethylsulfonyl)-5-(trifluoromethoxy)phenyl, 3-(trifluoromethoxy)- 5-(trifluoromethylsulfonyl)phenyl, 3-(trifluoromethoxy)phenyl, 3-(trifluoromethyl)phenyl, 3,5-bis(difluoromethoxy)phenyl, 3,5-bis (trifluoromethoxy)phenyl, 3,5-bis(trifluoromethyl)phenyl, 3,5-bis(trifluoromethylsulfonyl)phenyl, 3-bromo-5-(1,1,2, 2-tetrafluoroethoxy) phenyl, 3-bromo-5- (2,2-dichlorocyclopropyl) phenyl, 3-bromo-5- (difluoromethoxy) phenyl, 3-bromo-5- (trifluoromethoxy)phenyl, 3-chloro-5-(1,1,2,2-tetrafluoro-2-iodoethoxy)phenyl, 3-chloro-5-(1,1,2,2 -Tetrafluoroethoxy)phenyl, 3-chloro-5-(4-chlorophenyl)sulfonylphenyl, 3-chloro-5-(difluoromethylsulfonyl)phenyl, 3-chloro-5-(trifluoro) lomethoxy) phenyl, 3-chloro-5- (trifluoromethyl) phenyl, 3-chloro-5- (trifluoromethylsulfonyl) phenyl, 3-chloro-5- (trifluoromethylthio) phenyl, 3-cyano-5- (trifluoromethoxy) phenyl, 3-cyclopropyl-5- (difluoromethoxy) phenyl, 3-cyclopropyl-5- (trifluoromethoxy) phenyl, 3-cyclopropyl alcohol Phonyl-5- (trifluoromethoxy) phenyl, 3-fluoro-5- (trifluoromethoxy) phenyl, 3-methylsulfonyl-5- (trifluoromethoxy) phenyl, 3-methylsulfonyl-5 -(trifluoromethyl)phenyl or 2-chloro-6-(1-cyanocyclopropyl)pyridin-4-yl;

R ³ is -CN, aminocarbonyl, methylcarbamoyl, [ethyl(methyl)amino]carbonyl, [isopropyl(methyl)amino]carbonyl or [cyclopropylmethyl(methyl)amino]carbonyl;

R ⁴ is hydrogen, methyl or cyclopropyl.

Also further preferred (configuration 3-2) are compounds of formula (I), wherein

X is O;

R ¹ is hydrogen;

R ² is (3-fluorophenyl), (3-iodophenyl), (3,5-dibromophenyl), (3,5-dichlorophenyl), (3-chloro-5-methylsulfonylphenyl) ), 3-bromo-5-methylsulfonylphenyl, (3-cyano-5-fluorophenyl), 3-chloro-5-cyanophenyl, 3-bromo-5-cyanophenyl, 3, 5-dicyanophenyl, 3-(1,1,2,2-tetrafluoroethylthio)phenyl, 3-(1-cyanocyclopropyl)-5-(trifluoromethoxy)phenyl, 3-(di Fluoromethoxy)-5-fluorophenyl, 3-(difluoromethoxy)-5-iodophenyl, 3-(difluoromethylsulfonyl)-5-(trifluoromethoxy)phenyl, 3-( Trifluoromethoxy) -5- (trifluoromethylsulfonyl) phenyl, 3- (trifluoromethoxy) phenyl, 3- (trifluoromethyl) phenyl, 3- (trifluoromethylsulfonyl) phenyl, 3,5-bis (difluoromethoxy) phenyl, 3- (2-fluoropropan-2-yl) -5- (trifluoromethoxy) phenyl, 3,5-bis (trifluoromethoxy) phenyl, 3,5-bis (difluoromethyl) phenyl, 3,5-bis (trifluoromethyl) phenyl, 3- (difluoromethoxy) -5- (trifluoromethoxy) phenyl, 3,5-bis (difluoromethylsulfonyl)phenyl, 3,5-bis(trifluoromethylsulfonyl)phenyl, 3-bromo-5-(1,1,2,2-tetrafluoroethoxy)phenyl, 3 -Bromo-5-(2,2-dichlorocyclopropyl)phenyl, 3-bromo-5-(difluoromethoxy)phenyl, 3-bromo-5-(trifluoromethoxy)phenyl, 3-chloro -5- (1,1,2,2-tetrafluoro-2-iodoethoxy) phenyl, 3-chloro-5- (1,1,2,2-tetrafluoroethoxy) phenyl, 3- Chloro-5-(4-chlorophenyl)sulfonylphenyl, 3-chloro-5-(difluoromethylsulfonyl)phenyl, 3-chloro-5-(trifluoromethoxy)phenyl, 3-chloro-5- (trifluoromethyl)phenyl, 3-chloro-5-(1,1-difluoroethyl)phenyl, 3-chloro-5-(chlorodifluoromethyl)phenyl, 3-chloro-5-(trifluoro) Romethylsulfonyl) phenyl, 3-bromo-5- (trifluoromethylsulfonyl) phenyl, 3-chloro-5- (trifluoromethylthio) phenyl, 3-cyano-5- (trifluoromethyl) Toxy)phenyl, 3-cyclopropyl-5-(difluoromethane Koxy) phenyl, 3-cyclopropyl-5- (trifluoromethoxy) phenyl, 3-cyclopropylsulfonyl-5- (trifluoromethoxy) phenyl, 3-fluoro-5- (trifluoromethoxy) phenyl , 3-methylsulfonylphenyl, 3-(difluoromethoxy)-5-methylsulfanylphenyl, 3-(difluoromethoxy)-5-methylsulfonylphenyl, 3-methylsulfonyl-5-(tri) Fluoromethoxy) phenyl, 3-methylsulfonyl-5- (trifluoromethyl) phenyl, 2,6-dibromopyridin-4-yl, 2- (trifluoromethoxy) pyridin-4-yl, 2 -Chloro-6-(trifluoromethoxy)pyridin-4-yl, 2-bromo-6-methylsulfonyl-pyridin-4-yl or 2-chloro-6-(1-cyanocyclopropyl)pyridine- is 4-day;

R ³ is -CN, aminocarbonyl, methylcarbamoyl, ethylcarbamoyl, (isopropylamino)carbonyl, (difluoroethylamino)carbonyl, (3,3,3-trifluoropropylamino)carbonyl; carbonyl, (cyclopropylamino)carbonyl, dimethylaminocarbonyl, [ethyl(methyl)amino]carbonyl, [isopropyl(methyl)amino]carbonyl or [cyclopropylmethyl(methyl)amino]carbonyl;

R ⁴ is hydrogen, methyl or cyclopropyl.

In a further preferred embodiment, the present invention relates to formula (I'):

In the formula, structural components R ¹ , R ² , R ³ and R ⁴ have the meaning given in construction (1-1) or the meaning given in construction (2-1) or the meaning given in construction (3-1) or construction (1- 2) has the meaning provided in the meaning or configuration (2-2) or the meaning provided in the configuration (3-2).

In a further preferred embodiment, the invention relates to compounds of formula (I"), wherein R ¹ is hydrogen:

In the formula, the structural components R ² , R ³ and R ⁴ have the meaning given in construction (1-1) or the meaning given in construction (2-1) or the meaning given in construction (3-1) or construction (1-2). It has the meaning provided in the meaning or construction (2-2) provided or the meaning provided in the construction (3-2).

In a further preferred embodiment, the invention relates to compounds of formula (I″′), wherein R ¹ is hydrogen:

In the formula, the structural components R ² , R ³ and R ⁴ have the meaning given in construction (1-1) or the meaning given in construction (2-1) or the meaning given in construction (3-1) or construction (1-2). It has the meaning provided in the meaning or construction (2-2) provided or the meaning provided in the construction (3-2).

According to a further aspect, the present invention encompasses intermediate compounds useful for the preparation of compounds of formula (I).

In particular, the present invention encompasses intermediate compounds of formula (a) and salts thereof:

In the formula, R ¹ , R ³ and R ⁴ are the meaning provided in configuration (1-1) or the meaning provided in configuration (2-1) or the meaning provided in configuration (3-1) or the meaning provided in configuration (1-2) Or has the meaning provided in the configuration (2-2) or the meaning provided in the configuration (3-2).

In particular, the present invention covers the intermediate compound(s) INT-1 to INT-23, free amines in the case of amines and acids and also in the case of their salts and amine hydrochlorides (see Table 2):

INT-1: 6-[5-(1-aminoethyl)-1H-1,2,4-triazol-1-yl]pyrimidine-4-carbonitrile hydrochloride

INT-2: tert-butyl {1-[1-(6-cyanopyrimidin-4-yl)-1H-1,2,4-triazol-5-yl]ethyl}carbamate

INT-3: tert-butyl N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate

INT-4: 6-[5-[(1S)-1-aminoethyl]-1,2,4-triazol-1-yl]pyrimidine-4-carbonitrile;2,2,2-trifluoro acetic acid

INT-5: tert-butyl N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-5-methyl-1,2,4-triazol-3-yl]ethyl ]Carbamate

INT-6: 6-[5-[(1S)-1-aminoethyl]-3-methyl-1,2,4-triazol-1-yl]pyrimidine-4-carbonitrile hydrochloride

INT-7: tert-butyl N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl] ethyl]-carbamate

INT-8: 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carbonitrile hydrochloride

INT-9: 6-[5-[(1S)-1-aminoethyl]-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride

INT-10: 6-[5-[(1S)-1-aminoethyl]-3-methyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride

INT-11: 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride

INT-17: methyl 6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine- 4-carboxylate

INT-18: tert-butyl N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl] ethyl] carbamate

INT-19: tert-Butyl N-[(1S)-1-[5-cyclopropyl-2-[6-(methylcarbamoyl)pyrimidin-4-yl]-1,2,4-triazole-3 -yl]ethyl]carbamate

INT-20: tert-Butyl N-[(1S)-1-[5-cyclopropyl-2-[6-(dimethylcarbamoyl)pyrimidin-4-yl]-1,2,4-triazole-3 -yl]ethyl]carbamate

INT-21: 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]-N-methyl-pyrimidine-4-carboxyl Mead Hydrochloride

INT-22: 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]-N,N-dimethyl-pyrimidine-4- Carboxamide Hydrochloride

INT-12: 2-chloro-6- (1-cyanocyclopropyl) pyridine-4-carboxylic acid

INT-13: 3-(trifluoromethoxy)-5-(trifluoromethylsulfonyl)benzoic acid

INT-14: 3-bromo-5- (2,2-dichlorocyclopropyl) benzoic acid

INT-15: 3-bromo-5- (1,1,2,2-tetrafluoroethoxy) benzoic acid

INT-16: 3-(1-fluoro-1-methyl-ethyl)-5-(trifluoromethoxy)benzoic acid

INT-23: 3,5-bis(difluoromethylsulfonyl)benzoic acid

The compounds of formula (I) may possibly also, depending on the nature of the substituents, be in the form of stereoisomers, ie geometric and/or optical isomers or isomeric mixtures of varying composition. The present invention is generally only the compounds of formula (I) discussed herein, but may also provide both pure stereoisomers and any desired mixtures of these isomers.

However, according to the present invention it is preferred to use the optically active, stereoisomeric forms of the compounds of formula (I) and salts thereof.

Therefore, the present invention relates to both pure enantiomers and diastereomers and mixtures thereof for controlling pests, including arthropods and especially insects.

If appropriate, the compounds of formula (I) may exist in various polymorphic forms or mixtures of various polymorphic forms. Both pure polymorphs and mixtures of polymorphs are provided by and may be used in accordance with the present invention.

Justice

Those skilled in the art will understand that, unless expressly specified, the expression "a" or "an" as used in this application may mean "one (1)", "one (1) or more" or "at least one (1)", depending on the context. I know it can mean

For all structures described herein, such as ring systems and groups, adjacent atoms must not be -O-O- or -O-S-.

A structure with a variable number of possible carbon atoms (C atoms) may be referred to herein as _{a lower} C _{carbon atom- upper} C carbon atom structure (C _LL -C _UL structure) in this application for more specific definition. . Example: An alkyl group can consist of 3 to 10 carbon atoms, in which case it corresponds to a C ₃ -C ₁₀ alkyl. Ring structures composed of carbon atoms and heteroatoms may be referred to as “LL- to UL-member” structures. An example of a 6-membered ring structure is toluene (a 6-membered ring structure substituted with a methyl group).

If a generic term for a substituent, e.g. C _LL -C _UL alkyl, is present at the end of a composite substituent, e.g. C _LL -C _UL cycloalkyl-C _LL -C _UL alkyl, a composite substituent, e.g. C _LL The moiety at the beginning of -C _UL cycloalkyl may be identically or differently and independently monosubstituted or polysubstituted by the latter substituent, for example, C _LL -C _UL alkyl. All generic terms used in this application for chemical groups, cyclic systems and cyclic groups may be more specifically defined through the addition of "C _LL -C _UL " or "LL- to UL-one".

In the definitions of the symbols provided in the above formulas, generic terms representing the following substituents are generally used:

Halogen relates to the 7th main group element, preferably fluorine, chlorine, bromine and iodine, more preferably fluorine, chlorine and bromine, and even more preferably fluorine and chlorine.

Examples of heteroatoms are N, O, S, P, B, Si. Preferably, the term “heteroatoms” relates to N, S and O.

According to the present invention, "alkyl" by itself or as part of a chemical group is preferably a straight-chain or branched hydrocarbon having from 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n -Butyl, isobutyl, s-butyl, t-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethyl Propyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylpropyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl and 2-ethylbutyl. Preference is also given to alkyl having from 1 to 4 carbon atoms, such as in particular methyl, ethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl. Alkyl of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "alkenyl" by itself or as part of a chemical group is preferably a straight-chain or branched hydrocarbon having from 2 to 6 carbon atoms and at least one double bond, for example vinyl, 2-pro Phenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2 -butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3 -Pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl , 1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl, 2,2-dimethyl -3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl- 2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and 1-ethyl-2-methyl-2- represents propenyl. Preference is also given to alkenyl having from 2 to 4 carbon atoms, such as especially 2-propenyl, 2-butenyl or 1-methyl-2-propenyl. Alkenyls of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "alkynyl" as part of a chemical group or by itself means a straight-chain or branched hydrocarbon, preferably having from 2 to 6 carbon atoms and at least one triple bond, for example 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-buty Nyl, 1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl , 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl- 4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl -3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl and 2,5-hexadiynyl. Also preferred are alkynyls having 2 to 4 carbon atoms, such as in particular ethynyl, 2-propynyl or 2-butynyl-2-propenyl. Alkynyls of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "cycloalkyl" by itself or as part of a chemical group is preferably a monocyclic, bicyclic or tricyclic hydrocarbon having 3 to 10 carbons, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl or adamantyl. Preference is also given to cycloalkyls having 3, 4, 5, 6 or 7 carbon atoms such as, in particular, cyclopropyl or cyclobutyl. Cycloalkyls of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "alkylcycloalkyl" refers to monocyclic, bicyclic or tricyclic alkylcycloalkyl having 4 to 10 or 4 to 7 carbon atoms, for example methylcyclopropyl, ethylcyclopropyl, isopropyl Cyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. Preference is also given to alkylcycloalkyls having 4, 5 or 7 carbon atoms such as, in particular, ethylcyclopropyl or 4-methylcyclohexyl. Alkylcycloalkyls of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "cycloalkylalkyl" is preferably a monocyclic, bicyclic or tricyclic cycloalkylalkyl having 4 to 10 or 4 to 7 carbon atoms, for example cyclopropylmethyl, cyclobutylmethyl, Cyclopentylmethyl, cyclohexylmethyl and cyclopentylethyl. Preference is also given to cycloalkylalkyl having 4, 5 or 7 carbon atoms, such as, in particular, cyclopropylmethyl or cyclobutylmethyl. Cycloalkylalkyl of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "hydroxyalkyl" is preferably a straight-chain or branched alcohol having from 1 to 6 carbon atoms, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s- butanol and t-butanol. Preference is also given to hydroxyalkyl groups having 1 to 4 carbon atoms. A hydroxyalkyl group of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "alkoxy" is preferably straight-chain or branched O-alkyl having from 1 to 6 carbon atoms, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy , isobutoxy, s-butoxy and t-butoxy. Also preferred are alkoxy groups having 1 to 4 carbon atoms. Alkoxy groups of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "alkylthio", or "alkylsulfanyl" is preferably straight-chain or branched S-alkyl having from 1 to 6 carbon atoms, for example methylthio, ethyl, n-propylthio, iso Propylthio, n-butylthio, isobutylthio, s-butylthio and t-butylthio are shown. Preference is also given to alkylthio groups having 1 to 4 carbon atoms. Alkylthio groups of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "alkylsulfinyl" is preferably a straight-chain or branched alkylsulfinyl having 1 to 6 carbon atoms, for example methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl Represents n-butylsulfinyl, isobutylsulfinyl, s-butylsulfinyl and t-butylsulfinyl. Also preferred are alkylsulfinyl groups having 1 to 4 carbon atoms. Alkylsulfinyl groups of the present invention may be substituted by one or more identical or different radicals and encompass both enantiomers.

According to the present invention, "alkylsulfonyl" is preferably a straight-chain or branched alkylsulfonyl having from 1 to 6 carbon atoms, for example methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl phonyl, n-butylsulfonyl, isobutylsulfonyl, s-butylsulfonyl and t-butylsulfonyl. Also preferred are alkylsulfonyl groups having 1 to 4 carbon atoms. Alkylsulfonyl groups of the present invention may be substituted by one or more of the same or different radicals.

According to the present invention, "cycloalkylthio" or "cycloalkylsulfanyl" is preferably -S-cycloalkyl having 3 to 6 carbon atoms, for example cyclopropylthio, cyclobutylthio, cyclopentylthio, represents cyclohexylthio. Preferred are cycloalkylthio groups having 3 to 5 carbon atoms. Cycloalkylthio groups of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "cycloalkylsulfinyl" is preferably -S(O)-cycloalkyl having 3 to 6 carbon atoms, for example cyclopropylsulfinyl, cyclobutylsulfinyl, cyclopentylsulfinyl, represents cyclohexylsulfinyl. Also preferred are cycloalkylsuphinyl groups having 3 to 5 carbon atoms. Cycloalkylsulfinyl groups of the present invention may be substituted by one or more identical or different radicals and may encompass both enantiomers.

According to the invention, "cycloalkylsulfonyl" is preferably -SO ₂ -cycloalkyl having 3 to 6 carbon atoms, eg cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, cyclohexyl represents sylsulfonyl. Preferred are cycloalkylsulfonyl groups having 3 to 5 carbon atoms. Cycloalkylsulfonyl groups of the present invention may be substituted by one or more identical or different radicals.

According to the present invention "phenylthio", or "phenylsulfanyl" refers to -S-phenyl, for example phenylthio. A phenylthio group of the present invention may be substituted by one or more identical or different radicals.

According to the present invention "phenylsulfinyl" refers to -S(O)-phenyl, eg phenylsulfinyl. The phenylsulfinyl groups of the present invention may be substituted by one or more identical or different radicals, encompassing both enantiomers.

According to the invention "phenylsulfonyl" denotes -SO ₂ -phenyl eg phenylsulfonyl. A phenylsulfonyl group of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "alkylcarbonyl" is preferably a straight-chain or branched alkyl-C(=O) having 2 to 7 carbon atoms such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropyl carbonyl, s-butylcarbonyl and t-butylcarbonyl. Preference is also given to alkylcarbonyls having from 1 to 4 carbon atoms. Alkylcarbonyls of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "alkoxycarbonyl" alone or as a component of a chemical group is preferably a straight-chain or branched alkoxycarbonyl having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkoxy moiety, e.g. For example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, s-butoxycarbonyl and t-butoxycarbonyl are shown. Alkoxycarbonyl groups of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "alkylaminocarbonyl" is preferably a straight-chain or branched alkylaminocarbonyl having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl moiety, for example methylaminocarbonyl , ethylaminocarbonyl, n-propylaminocarbonyl, isopropylaminocarbonyl, s-butylaminocarbonyl and t-butylaminocarbonyl. Alkylaminocarbonyl groups of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, “ N,N -dialkylaminocarbonyl” is preferably a straight-chain or branched N,N -dialkylaminocarb having from 1 to 6 carbon atoms or from 1 to 4 carbon atoms in the alkyl moiety. Carbonyl, for example N,N -dimethylaminocarbonyl, N,N -diethylaminocarbonyl, N,N -di(n-propylamino)carbonyl, N,N -di(isopropylamino)carbonyl and N,N -di-(s-butylamino)carbonyl. The N,N -dialkylaminocarbonyl groups of the present invention may be substituted by one or more identical or different radicals.

According to the present invention, "aryl" is a monocyclic, bicyclic or polycyclic aromatic system having preferably 6 to 14, in particular 6 to 10, ring carbon atoms, for example phenyl, naphthyl, anthryl, represents phenanthrenyl, preferably phenyl. Aryl also refers to fused polycyclic systems such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenyl, wherein the bonding site is on the aromatic system. Aryl groups of the present invention may be substituted by one or more identical or different radicals.

An example of a substituted aryl is an arylalkyl, which may similarly be substituted by one or more identical or different radicals in the C ₁ -C ₄ alkyl and/or C ₆ -C ₁₄ aryl moiety. Examples of such arylalkyl include benzyl and phenyl-1-ethyl.

In accordance with the present invention, the term “polycyclic” ring refers to ring systems linked through single or double bonds, including fused, bridged, and spirocyclic carbocyclic and heterocyclic rings.

According to the present invention, "heterocycle", "heterocyclic ring" or "heterocyclic ring system" means that at least one carbon atom consists of a heteroatom, preferably N, O, S, P, B, Si, Se represents a carbocyclic ring system which is substituted by a heteroatom from the group, is saturated, unsaturated or heteroaromatic and has at least one ring which may be unsubstituted or substituted, wherein the bonding site is on a ring atom. Unless otherwise defined, a heterocyclic ring preferably has 3 to 9 ring atoms, in particular 3 to 6 ring atoms, and at least one, preferably 1 to 4, especially 1, 2 ring atoms in the heterocyclic ring. contains two or three heteroatoms, preferably selected from the group consisting of N, O, and S, but the two oxygen atoms must not be directly adjacent. Heterocyclic rings generally contain no more than 4 nitrogen atoms and/or no more than 2 oxygen atoms and/or no more than 2 sulfur atoms. In the case of optionally substituted heterocyclyl, the present invention also relates to polycyclic ring systems such as 8-azabicyclo[3.2.1]octanyl, 1-azabicyclo[2.2.1]heptyl, 1-oxa -5-azaspiro[2.3]hexyl or 2,3-dihydro-1 H -indole.

Heterocyclyl groups of the present invention include, for example, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, pyrrolinyl, pyrrolidinyl, imidazolinyl, imidazolidinyl, thiazolidinyl, oxazolidinyl, dioxolanil, dioxolyl, pyrazolidinyl, tetrahydrofuranil, dihydrofuranil, oxetanil, oxiranil, azetidinyl, aziridinyl, oxazetidinyl, oxaziridinyl, oxazepanil, oxazinanyl, azepanil, oxopyrrolidinyl, dioxopyrrolidinyl, oxomorpholinyl, oxopiperazinyl and oxepanil.

Of particular interest are heteroaryls, i.e. heteroaromatics. According to the present invention, the term heteroaryl denotes a heteroaromatic compound, ie a fully unsaturated aromatic heterocyclic compound belonging to the above definition of heterocycle. Preference is given to 5- to 7-membered rings having 1 to 3, preferably 1 or 2 identical or different heteroatoms from the above groups. Heteroaryls of the present invention include, for example, furyl, thienyl, pyrazolyl, imidazolyl, 1,2,3- and 1,2,4-triazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1 ,2,3-, 1,3,4-, 1,2,4- and 1,2,5-oxadiazolyl, azepinyl, pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl , 1,3,5-, 1,2,4- and 1,2,3-triazinyl, 1,2,4-, 1,3,2-, 1,3,6- and 1,2,6 -oxazinil, oxepinil, thiepinil, 1,2,4-triazolonil and 1,2,4-diazepinyl. Heteroaryl groups of the present invention may also be substituted by one or more identical or different radicals.

In accordance with the present invention, the substituent =O (oxo) may replace two hydrogen atoms of a methylene (CH ₂ ) group or a lone pair of sulfur, nitrogen and phosphorus atoms bearing only substituents other than hydrogen. A radical C ₂ -alkyl, for example, becomes, for example, —COCH ₃ through substitution by =O (oxo), while a heterocycle thietan-3-yl-, for example, by one =O (oxo) group. 1-oxothietan-3-yl through substitution or 1,1-dioxothietan-3-yl through substitution of two =O (oxo) groups.

According to the invention, the substituent =S (thiono) can substitute two hydrogen atoms of the methylene (CH ₂ ) group. For example the radical C ₂ -alkyl becomes —CSCH ₃ through substitution, for example by =S (thiono).

As used herein, the term "optionally substituted" means that an optionally substituted group is substituted with further substituents or is not substituted with further substituents.

The term “in each instance optionally substituted” refers to groups/substituents such as alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, cycloalkyl, aryl, phenyl, benzyl, heterocyclyl and hetero It is meant that an aryl radical is substituted, for example a substituted radical is derived from an unsubstituted base structure, wherein a substituent, for example one (1) substituent or a plurality of substituents, preferably 1, 2, 3, 4, 5, 6 or 7 are amino, hydroxyl, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, C ₁ -C ₄ carboxyl, carbonamide, SF ₅ , Aminosulfonyl, C ₁ -C ₄ Alkyl, C ₁ -C ₄ Haloalkyl, C ₃ -C ₄ Cycloalkyl, C ₂ -C ₄ Alkenyl, C ₅ -C ₆ Cycloalkenyl, C ₂ -C ₄ Alky Nyl, N- Mono-C ₁ -C ₄ Alkylamino, N,N- Di-C ₁ -C ₄ Alkylamino, N- C ₁ -C ₄ Alkanoylamino, C ₁ -C ₄ Alkoxy, C ₁ -C ₄ haloalkoxy, C ₂ -C ₄ alkenyloxy C ₂ -C ₄ alkynyloxy, C ₃ -C ₄ cycloalkoxy, C ₅ -C ₆ cycloalkenyloxy C ₁ -C ₄ alkoxycarbonyl, C ₂ - C ₄ alkenyloxycarbonyl, C ₂ -C ₄ alkynyloxycarbonyl, C ₆ -,C ₁₀ -,C ₁₄ -aryloxycarbonyl, C ₁ -C ₄ alkanoyl, C ₂ -C ₄ alkenyl Carbonyl, C ₂ -C ₄ Alkynylcarbonyl, C ₆ -,C ₁₀ -,C ₁₄ -Arylcarbonyl, C ₁ -C ₄ Alkylthio, C ₁ -C ₄ Haloalkylthio, C ₃ -C ₄ Cycloalkylthio, C ₂ -C ₄ alkenylthio, C ₅ -C ₆ cycloalkenylthio, C ₂ -C ₄ alkynylthio, C ₁ including both enantiomers of a C ₁ -C ₄ alkylsulfinyl group -C ₄ alkylsulfinyl, C ₁ -C ₄ haloalkylsulfinyl containing both enantiomers of _a haloalkylsulfinyl group, C ₁ -C ₄ alkylsulfonyl, C ₁ -C _{4 haloalkyl} Sulfonyl, N- Mono-C ₁ -C ₄ Alkylaminosulfonyl, N,N- di-C ₁ -C ₄ alkylaminosulfonyl, C ₁ -C ₄ alkylphosphinyl, including both enantiomers of C _{1 -C 4 alkylphosphinyl and C 1 -C 4 alkylphosphonyl ,} C ₁ -C ₄ Alkylphosphonyl, N- C ₁ -C ₄ Alkylaminocarbonyl, N,N -di-C ₁ -C ₄ Alkylaminocarbonyl, NC ₁ -C ₄ Alkanoylaminocarbonyl, NC ₁ -C ₄ Alka Noyl-NC ₁ -C ₄ Alkylaminocarbonyl, C ₆ -,C ₁₀ -,C ₁₄ -Aryl, C ₆ -,C ₁₀ -,C ₁₄ -Aryloxy, benzyl, benzyloxy, benzylthio, C ₆ - ,C ₁₀ -,C ₁₄ -arylthio, C ₆ -,C ₁₀ -,C ₁₄ -arylamino, benzylamino, heterocyclyl and trialkylsilyl, substituents connected via a double bond such as C ₁ -C ₄ alkyl is selected from the group consisting of a leadene (eg methylidene or ethylidene), an oxy group, an imino group and a substituted imino group. When two or more radicals form one or more rings, they may be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, for example containing an aromatic ring and having further substitution. The substituents mentioned by way of example (“the first level of substituents”) are, for example, halogen, hydroxyl, amino, nitro, cyano, isocyano, azido, acylamino, oxo groups, respectively, if they contain a hydrocarbonaceous component. and by one or more substituents independently selected from imino groups, may optionally have further substitution therein ("second level of substituents"). The term "(optionally) substituted" group preferably covers only one or two substituent levels.

Halogen-substituted chemical groups or halogenated groups (eg alkyl or alkoxy) of the present invention are mono- or polysubstituted by halogen up to the maximum possible number of substituents. Such groups are also referred to as halo groups (eg haloalkyl). In the case of polysubstitution by halogen, the halogen atoms may be the same or different, and may all be bonded to one carbon atom or may be bonded to multiple carbon atoms. Halogen is in particular fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine. More particularly, halogen-substituted groups are monohalocycloalkyl such as 1-fluorocyclopropyl, 2-fluorocyclopropyl or 1-fluorocyclobutyl, monohaloalkyl such as 2-chloroethyl, 2-fluoroethyl , 1-chloroethyl, 1-fluoroethyl, chloromethyl, or fluoromethyl; Perhaloalkyl such as trichloromethyl or trifluoromethyl or CF ₂ CF ₃ , polyhaloalkyl such as difluoromethyl, 2-fluoro-2-chloroethyl, dichloromethyl, 1,1,2,2-tetra fluoroethyl or 2,2,2-trifluoroethyl. Additional examples of haloalkyl are trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2 ,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2-chloro-2,2-difluoroethyl, pentafluoroethyl, 3,3,3-trifluoropropyl and pentafluoroethyl It is fluoro-t-butyl. Preference is given to haloalkyls having 1 to 4 carbon atoms and 1 to 9, preferably 1 to 5 identical or different halogen atoms selected from fluorine, chlorine and bromine. Particular preference is given to haloalkyls having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms selected from fluorine and chlorine, such as, in particular, difluoromethyl, trifluoromethyl or 2; 2-difluoroethyl. Further examples of halogen-substituted compounds include haloalkoxy such as OCF ₃ , OCHF ₂ , OCH ₂ F, OCF ₂ CF ₃ , OCH ₂ CF ₃ , OCH ₂ CHF ₂ and OCH ₂ CH ₂ Cl, haloalkylsulfanyl such as difluoro Romethylthio, trifluoromethylthio, trichloromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 1,1, 2,2-tetrafluoroethylthio, 2,2,2-trifluoroethylthio or 2-chloro-1,1,2-trifluoroethylthio, haloalkylsulfinyl such as difluoromethylsulfinyl, Trifluoromethylsulfinyl, trichloromethylsulfinyl, chlorodifluoromethylsulfinyl, 1-fluoroethylsulfinyl, 2-fluoroethylsulfinyl, 2,2-difluoroethylsulfinyl, 1, 1,2,2-tetrafluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl and 2-chloro-1,1,2-trifluoroethylsulfinyl, haloalkylsulfinyl such as difluoro Romethylsulfinyl, trifluoromethylsulfinyl, trichloromethylsulfinyl, chlorodifluoromethylsulfinyl, 1-fluoroethylsulfinyl, 2-fluoroethylsulfinyl, 2,2-difluoroethyl Sulfinyl, 1,1,2,2-tetrafluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl and 2-chloro-1,1,2-trifluoroethylsulfinyl, haloalkyl Sulfonyl groups such as difluoromethylsulfonyl, trifluoromethylsulfonyl, trichloromethylsulfonyl, chlorodifluoromethylsulfonyl, 1-fluoroethylsulfonyl, 2-fluoroethylsulfonyl, 2, 2-difluoroethylsulfonyl, 1,1,2,2-tetrafluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl and 2-chloro-1,1,2-trifluoro It is ethylsulfonyl.

In the case of radicals having carbon atoms, preference is given to those having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. Generally preferred are halogens, for example fluorine and chlorine, (C ₁ -C ₄ )alkyl, preferably methyl or ethyl, (C ₁ -C ₄ )haloalkyl, preferably trifluoromethyl, (C ₁ -C ₄ ) alkoxy, preferably methoxy or ethoxy, (C ₁ -C ₄ ) haloalkoxy, a substituent from the group of nitro and cyano. Particularly preferred herein are the substituents methyl, methoxy, fluorine and chlorine.

Substituted aminos such as mono- or disubstituted aminos are, for example, substituted aminos N- substituted by one or two identical or different radicals from the group of alkyl, hydroxy, amino, alkoxy, acyl and aryl. a radical from the group of radicals; preferably N- mono- and N,N -dialkylamino, (e.g. methylamino, ethylamino, N,N- dimethylamino, N,N -diethylamino, N,N- di-n-propylamino , N,N -diisopropylamino or N,N -dibutylamino), N- mono- or N,N -dialkoxyalkylamino groups (e.g. N -methoxymethylamino, N -methoxyethylamino) , N,N- di(methoxymethyl)amino or N,N -di(methoxyethyl)amino), N- mono- and N,N -diarylamino such as optionally substituted aniline, acylamino, N, N -diacylamino, N- alkyl- N- arylamino, N- alkyl- N- acylamino and also saturated N -heterocycles; Preference here is given to alkyl radicals having 1 to 4 carbon atoms; wherein aryl is preferably phenyl or substituted phenyl; If known, the definitions further provided below apply, preferably (C ₁ -C ₄ )-alkanoyl. The same applies to substituted hydroxylamino or hydrazino.

Substituted aminos also include quaternary ammonium compounds (salts) with four organic substituents on the nitrogen atom.

Optionally substituted phenyl is preferably halogen, (C ₁ -C ₄ )alkyl, (C ₁ -C ₄ )alkoxy, (C ₁ -C ₄ )alkoxy-(C ₁ -C ₄ )alkoxy, (C ₁ -C 4 )alkoxy ₄ )alkoxy-(C ₁ -C ₄ )alkyl, (C ₁ -C ₄ )haloalkyl, (C ₁ -C ₄ )haloalkoxy, (C ₁ -C ₄ )alkylthio, (C ₁ -C ₄ )haloalkylthio, (C ₁ -C ₄ )alkylsulfinyl (C ₁ -C ₄ ) haloalkylsulfinyl, (C ₁ -C ₄ ) alkylsulfonyl (C ₁ -C ₄ )haloalkylsulfonyl, mono- or polysubstituted, preferably up to tri-substituted by the same or different radicals from the group of cyano, isocyano and nitro, or unsubstituted phenyl, such as o-, m- and p-tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-fluorophenyl, 2-, 3- and 4- Trifluoromethyl- and 4-trichloromethylphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl, 4-heptafluoro It is lophenyl.

Optionally substituted cycloalkyl is preferably halogen, cyano, (C ₁ -C ₄ )alkyl, (C ₁ -C ₄ )alkoxy, (C ₁ -C ₄ )alkoxy-(C ₁ -C ₄ )alkoxy, ( by identical or different radicals from the group C ₁ -C ₄ )alkoxy-(C ₁ -C ₄ )alkyl, (C ₁ -C ₄ )haloalkyl and (C ₁ -C ₄ )haloalkoxy, in particular 1 cycloalkyl which is mono- or poly-substituted, preferably up to tri-substituted or unsubstituted, by two or two (C ₁ -C ₄ )alkyl radicals.

Compounds of the present invention may occur in preferred embodiments. Individual embodiments described herein may be combined with each other. Combinations that violate the laws of nature and would therefore be excluded by a person skilled in the art based on his/her expertise are not included. For example, ring structures with 3 or more adjacent oxygen atoms are excluded.

isomer

Depending on the nature of the substituents, the compounds of formula (I) may be in the form of geometrically and/or optically active isomers or mixtures of corresponding isomers of different composition. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. Thus, the present invention covers both pure stereoisomers and any mixtures of these isomers.

method and use

The present invention also relates to a method for controlling pests, wherein the compounds of formula (I) are allowed to act on pests and/or their habitat. Control of pests is preferably carried out in agriculture and forestry and material protection. Preferably methods for surgical or therapeutic treatment of the human or animal body and diagnostic methods performed on the human or animal body are excluded from this.

Furthermore, the present invention relates to the use of compounds of formula (I) as agrochemicals, in particular as crop protection agents.

In the context of the present application, the term "agrochemical" in each case also always includes the term "crop protection agent".

Compounds of formula (I), which have good plant tolerance, good thermotoxicity, and good environmental compatibility, can be used to protect plants and plant organs against biotic and abiotic stress agents, increase harvest yield, improve crop yield, crop quality, and Suitable for the control of pests, especially insects, arachnids, worms, especially nematodes and molluscs, protection of stocks and materials, and sanitation, encountered in agriculture, horticulture, animal husbandry, aquaculture, forestry, gardens and leisure facilities .

In the context of this patent application, the term "hygiene" has the purpose of preventing diseases, in particular infectious diseases, and/or serves to protect human and animal health, and/or protects the environment, and/or maintains cleanliness. It is understood to mean any and all measures, procedures, and practices that According to the invention, this is in particular the cleaning, disinfection and sterilization of, for example, textiles or hard surfaces, in particular glass, wood, concrete, porcelain, ceramics, plastics or also metal(s), and these are sanitary pests and/or their excrement Including measures to ensure that there is no Surgical or therapeutic treatment procedures preferably applicable to the human or animal body and diagnostic procedures performed on the human or animal body are excluded from the scope of the present invention in this regard.

Accordingly, the term "hygiene sector" refers to all areas, technical fields, and sectors of importance in relation to hygiene in kitchens, bakeries, airports, bathrooms, swimming pools, department stores, hotels, hospitals, stables, animal husbandry, etc., where these hygiene measures, procedures and practices are important. Covers industrial applications.

The term "sanitary pest" is therefore understood to mean one or more pests whose presence in the sanitary sector is a problem, in particular for health reasons. Therefore, in the hygiene sector, avoiding or minimizing the presence of, and/or exposure to, hygiene pests is a primary goal. This can be achieved, in particular, through the application of pesticides that can be used to prevent infection and to address pre-existing infections. Formulations that avoid or reduce exposure to pests may also be used. Hygiene pests include, for example, the organisms mentioned below.

Accordingly, the term “sanitary protection” encompasses all actions aimed at maintaining and/or improving these sanitary measures, procedures and practices.

The compounds of formula (I) can preferably be used as agrochemicals. They are generally active against sensitive and resistant species, and against all or some developing phases. The pests mentioned above include:

Pests from the phylum Arthropoda, in particular from the class Arachnida, for example Acarus spp., for example Acarus siro, Aceria kuko, Aceria seldoni (Aceria sheldoni), Aculops spp., Aculus spp., For example, Aculus fockeui, Aculus schlechtendali, Amblyomma ( Amblyomma) spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., for example, Brevipalpus po Brevipalpus phoenicis, Briobia gramineum, Briobia praetiosa, Centruroides spp., Chorioptes spp., Dermanisus gallina (Dermanyssus gallinae), Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp., Examples For example, Eotetranychus hicoriae, Epitrimerus pyri, Eutetranychus spp., For example, Eutetranychus banksi, Eriophyes spp., for example, Eriophyes pyri, Glycyphagus domesticus (Glycyphagus dom esticus), Halotydeus destructor, Hemitarsonemus spp., For example, Hemitarsonemus latus (= Polyphagotarsonemus latus ), Hyalomma spp., Ixodes spp., Latrodectus spp., Loxosceles spp., Neutrombicula autumnalis, Nu Nuphersa spp., Oligonychus spp., e.g., Oligonychus coffeae, Oligonychus coniferarum, Oligonychus illissis ilicis), Oligonychus indicus, Oligonychus mangiferus, Oligonychus pratensis, Oligonychus punicae, Oligonychus Io Oligonychus yothersi, Ornithodorus spp., Ornithonyssus spp., Panonychus spp., for example Panonychus citri (= meta Tetranychus citri), Panonychus ulmi (= Metatetranychus ulmi), Phyllocoptruta oleivora, Platitetranicus multidigituli (Platytetranychus multidigituli), Polyphagotarsonemus latus (Polyph agotarsonemus latus), Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Steneotarsonemus spp., Steneotarsonemus spinki, Tarsonemus spp., for example Tarsonemus confusus, Tarsonemus palli Tarsonemus pallidus, Tetranychus spp., for example, Tetranychus canadensis, Tetranychus cinnabarinus, Tetranychus turkestani ), Tetranychus urticae, Trombicula alfreddugesi, Vaejovis spp., Vasates lycopersici;

from Chilopoda, for example Geophilus spp., Scutigera spp.;

from the order Collembola or from the river, for example Onychiurus armatus, Sminthurus viridis;

from Diplopoda, for example Blaniulus guttulatus;

From Insecta, e.g. from Blattodea, e.g. Blatta orientalis, Blattella asahinai, Blattella germanica, Leucophae Leucophaea maderae, Loboptera decipiens, Neostylopyga rhombifolia, Panchlora spp., Parcoblatta spp., Perry Periplaneta spp., for example, Periplaneta americana, Periplaneta australasiae, Pycnoscelus surinamensis, Supella longipalpa longipalpa);

From the order Coleoptera, for example Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Aethina tumida, Agelastica alni, Agrilus spp., For example, Agrilus planipennis, Agrilus coxalis, Agrilus bilineatus (Agrilus bilineatus), Agrilus anxius, Agriotes spp., for example Agriotes linneatus, Agriotes mancus, Agriotes Agriotes obscurus, Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anomala dubia, Anoflophora ( Anoplophora) spp., e.g., Anoplophora glabripennis, Anthonomus spp., e.g., Anthonomus grandis, Anthrenus spp., Apion spp., Apogonia spp., Athous haemorrhoidales, Atomaria spp., for example Atomaria linearis , Attagenus spp., Baris caerulescens, Bruchidius obt ectus), Bruchus spp., for example, Bruchus pisorum, Bruchus rufimanus, Cassida spp., Cerotoma trifurcata , Ceutorrhynchus spp., for example, Ceutorrhynchus assimilis, Ceutorrhynchus quadridens, Ceutorrhynchus rapae, Caetoxnema (Chaetocnema) spp., for example, Chaetocnema confinis, Chaetocnema denticulata, Chaetocnema ectypa, Cleonus mendicus mendicus), Conoderus spp., Cosmopolites spp., for example, Cosmopolites sordidus, Costelytra zealandica, Ctenissera (Ctenicera) spp., Curculio spp., For example, Curculio caryae, Curculio caryatrypes, Curculio obtusus (Curculio obtusus), Curculio sayi, Cryptolestes ferrugineus, Cryptolestes pusillus, Cryptohynchus lapathi, Cryptohynchus mangifera (Cryptorhynchus mangiferae), Cylindrocopturus spp., Cylindrocopturus Adsper Cylindrocopturus adspersus, Cylindrocopturus furnissi, Dendroctonus spp., for example Dendroctonus ponderosae, Dermestes spp. , Diabrotica spp., for example, Diabrotica balteata, Diabrotica barberi, Diabrotica undecimpunctata howardi, Diabrotica undecimpunctata undecimpunctata, Diabrotica virgifera virgifera, Diabrotica virgifera zeae, decochrossis ( Dichocrocis) spp., Dicladispa armigera, Diloboderus spp., Epicaerus spp., Epilacna spp., For example, Epilacna borera Epilacna borealis, Epilacna varivestis, Epitrix spp., for example Epitrix cucumeris, Epitrix fuscula, Epitrix hir Epitrix hirtipennis, Epitrix subcrinita, Epitrix tuberis, Faustinus spp., Gibbium psylloides, Cnatocerus cornu Gnathocerus co rnutus), Hellula undalis, Heteronychus arator, Heteronyx spp., Hoplia argentea, Hylamorpha elegans ), Hylotrupes bajulus, Hypera postica, Hypomeces squamosus, Hypotenemus spp., For example, Hippotenemus hampei (Hypothenemus hampei), Hippotenemus obscurus, Hippotenemus pubescens, Lachnosterna consanguinea, Lasioderma sericorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa decemlineata, Leucoptera spp., for example, Leucoptera coffeella, Limonius ectypus, Lissorhoptrus oryzophilus, Listronotus (= Hyperodes) spp., Li Lixus spp., Luperodes spp., Luperomorpha xanthodera, Lyctus spp., Megacyllene spp., for example, Megasilene Robinia (Megacyllene robiniae), Megascelis spp., Melanotu s) spp., e.g. Melanotus longulus oregonensis, Meligethes aeneus, Melolontha spp., e.g. Melolontha melolonta (Melolontha melolontha), Migdolus spp., Monochamus spp., Naupactus xanthographus, Necrobia spp., Neogalerucella spp ., Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Othiorincus ( Otiorhynchus) spp., for example, Otiorhynchus cribricollis, Otiorhynchus ligustici, Otiorhynchus ovatus, Otiorhynchus rugosutriarus (Otiorhynchus rugosostriarus), Otiorhynchus sulcatus, Oulema spp., For example, Oulema melanopus, Oulema oryzae, Oxysetonia zukunda ( Oxycetonia jucunda), Phaedon cochleariae, Phyllophaga spp., Phyllophaga helleri, Phyllotreta spp., For example, Phyllotreta Phyllotreta armoraciae, Phyllotreta pus illa), Phyllotreta ramosa, Phyllotreta striolata, Popillia japonica, Premnotrypes spp., Prostephanus truncatus ), Psylliodes spp., for example, Psylliodes affinis, Psylliodes chrysocephala, Psylliodes punctulata, Pthinus ( Ptinus) spp., Rhizobius ventralis, Rhizopertha dominica, Rhynchophorus spp., Rhynchophorus ferrugineus, Rhynchophorus palmarum ( Rhynchophorus palmarum), Scolytus spp., For example, Scolytus multistriatus, Sinoxylon perforans, Sitophilus spp., For example , Sitophilus granarius, Sitophilus linearis, Sitophilus oryzae, Sitophilus zeamais, Sphenophorus spp. , Stegobium paniceum, Sternechus spp., for example, Sternechus paludatus, Symphyletes spp., Tanymecus spp. ., For example, Tanimecus dilaticolis (Tany mecus dilaticollis), Tanymecus indicus, Tanymecus palliatus, Tenebrio molitor, Tenebrioides mauretanicus, trivolium ( Tribolium) spp., e.g., Tribolium audax, Tribolium castaneum, Tribolium confusum, Trogoderma spp., Tikius (Tychius) spp., Xylotrechus spp., Zabrus spp., for example Zabrus tenebrioides;

from Dermaptera, for example Anisolabis maritime, Forficula auricularia, Labidura riparia;

From the order Diptera, for example Aedes spp., for example Aedes aegypti, Aedes albopictus, Aedes sticticus ), Aedes vexans, Agromyza spp., For example, Agromyza frontella, Agromyza parvicornis, Anastrepha spp ., Anopheles spp., for example, Anopheles quadrimaculatus, Anopheles gambiae, Asphondylia spp., Bactrocera spp., For example, Bactrocera cucurbitae, Bactrocera dorsalis, Bactrocera oleae, Bibio hortulanus, Caliphora Eri Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chironomus spp., Chrysomya spp., Chrysops ( Chrysops) spp., Chrysozona pluvialis, Cochliomya spp., Contarinia spp., for example Contarinia johnsoni, Contari Contarinia nasturtii, Contarinia pyrivora, Contarinia schulzi, Contarinia Contarinia sorghicola, Contarinia tritici, Cordylobia anthropophaga, Cricotopus sylvestris, Culex spp., For example, Culex pipiens, Culex quinquefasciatus, Culicoides spp., Culiseta spp., Cuterebra spp., Dacus oleae, Dasineura spp., eg Dasineura brassicae, Delia spp., eg Delia antiqua (Delia) antiqua), Delia coarctata, Delia florilega, Delia platura, Delia radicum, Dermatobia hominis, Drosophila ( Drosophila) spp., e.g., Drosphila melanogaster, Drosophila suzukii, Echinocnemus spp., Euleia heraclei, Pannia (Fannia) spp., Gasterophilus spp., Glossina spp., Haematopota spp., Hydrellia spp., Hydrellia griseola griseola), Hylemya spp., Hippobosca spp., Hypoderma spp., Liriomyza spp., For example, Liriomyza brassicae, Liriomyza huidobrensis, Liriomyza sativae, Lucilia spp., For example, Lucilia cuprina cuprina), Lutzomyia spp., Mansonia spp., Musca spp., for example, Musca domestica, Musca domestica vicina ), Oestrus spp., Oscinella frit, Paratanytarsus spp., Paralauterborniella subcincta, Pegomia or Pegomia Pegomyia spp., for example, Pegomya betae, Pegomya hyoscyami, Pegomya rubivora, Phlebotomus spp., Phorbia spp., Phormia spp., Piophila casei, Platyparea poeciloptera, Prodiplosis spp., Psila Rosae rosae), Rhagoletis spp., for example, Rhagoletis cingulata, Rhagoletis completa, Rhagoletis fausta, Rhagoletis indiferens indifferens), Rhagoletis mendax, and Rhagoletis pomonel la), Sarcophaga spp., Simulium spp., For example, Simulium meridionale, Stomoxys spp., Tabanus spp. , Tetanops spp., Tipula spp., For example, Tipula paludosa, Tipula simplex, Toxotrypana curvicauda );

From the order Hemiptera, for example Acizzia acaciae baileyanae, Acizzia dodonaeae, Acizzia uncatoides, Acrid two Rita (Acrida turrita), Acyrthosipon spp., For example, Acyrthosiphon pisum, Acrogonia spp., Aeneolamia spp., Agonossena (Agonoscena) spp., Aleurocanthus spp., Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus , Allocaridara malayensis, Amrasca spp., For example, Amrasca bigutulla, Amrasca devastans, Anuraphis cardui , Aonidiella spp., For example, Aonidiella aurantii, Aonidiella citrina, Aonidiella inornata, Aphanostigma piri, Aphis spp., for example Aphis citricola, Aphis craccivora, Aphis fabae, Aphis forbesi ), Aphis glycines, Aphis gossypii, Aphis hederae (Aphi s hederae), Aphis illinoisensis, Aphis middletoni, Aphis nasturtii, Aphis nerii, Aphis pomi, Aphis spiraechola (Aphis spiraecola), Aphis viburniphila, Arboridia apicalis, Arytainilla spp., Aspidiella spp., Aspidiotus spp., for example , Aspidiotus nerii, Atanus spp., Aulacorthum solani, Bemisia tabaci, Blastopsylla occidentalis, bore Boreioglycaspis melaleucae, Brachycaudus helichrysi, Brachycolus spp., Brevicoryne brassicae, Cacopsylla spp. , For example, Cacopsylla pyricola, Calligypona marginata, Capulinia spp., Carneocephala fulgida, Ceratovacuna lanigera ), Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita Onuki (Chlorita onukii), condra Chondracris rosea, Chromaphis juglandicola, Chrysomphalus aonidum, Chrysomphalus ficus, Cicadulina mbila, Coco Coccomytilus halli, Coccus spp., For example, Coccus hesperidum, Coccus longulus, Coccus pseudomagnoliarum, Coccus viridis, Cryptomyzus ribis, Cryptoneossa spp., Ctenarytaina spp., Dalbulus spp., Diareurodes Kidendane Dialeurodes chittendeni, Dialeurodes citri, Diaphorina citri, Diaspis spp., Diuraphis spp., Doralis spp ., Drosicha spp., Dysaphis spp., for example, Dysaphis apiifolia, Dysaphis plantaginea, Dysaphis tulipae ), Dysmicoccus spp., Empoasca spp., for example, Empoasca abrupta, Empoasca fabae, Empoasca maligna , Empoasca solana, Empoasca stevensi, Eriosoma (Eriosoma) spp., For example, Eriosoma amerianum, Eriosoma lanigerum, Eriosoma pyricola, Erythroneura spp. , Eucalyptolyma spp., Euphyllura spp., Euscelis bilobatus, Ferrisia spp., Fiorinia spp., Purcaspis Oceanica (Furcaspis oceanica), Geococcus coffeae, Glycaspis spp., Heteropsylla cubana, Heteropsylla spinulosa, Homalodisca Homalodisca coagulata, Hyalopterus arundinis, Hyalopterus pruni, Icerya spp., For example, Icerya purchasi ), Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., For example, Lecanium corni ( Lecanium corni) (= Parthenolecanium corni), Lepidosaphes spp., For example, Lepidosaphes ulmi, Lipaphis erysimi, Ropoleu Lopholeucaspis japonica, Lycorma delicatula, Macrosiphum spp., for example For example, Macrosiphum euphorbiae, Macrosiphum lilii, Macrosiphum rosae, Macrosteles facifrons, Mahanarva spp., Melanapis Inc. Melanaphis sacchari, Metcalfiella spp., Metcalfa pruinosa, Metopolophium dirhodum, Monellia costalis, Monelliopsis pecca Monelliopsis pecanis, Myzus spp., for example Myzus ascalonicus, Myzus cerasi, Myzus ligustri, Myzus orna Myzus ornatus, Myzus persicae, Myzus nicotianae, Nasonovia ribisnigri, Neomaskellia spp., Nepotetics (Nephotettix) spp., for example, Nephotettix cincticeps, Nephotettix nigropictus, Nettigoniclla spectra, Nilaparvata lugens , Oncometopia spp., Orthezia praelonga, Oxya chinensis, Pachypsylla spp., Parabemisia myricae, Paratrio Paratrioza spp., for example, Paratrioza cockerel Lee (Paratrioza cockerelli), Parlatoria spp., Pemphigus spp., For example, Pemphigus bursarius, Pemphigus populivenae , Peregrinus maidis, Perkinsiella spp., Phenacoccus spp., for example, Phenacoccus madeirensis, Phloeomijus passeri Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., for example Phyloxera devastatrix, Phylloxera notabilis, Phylloxera asphidistra (Pinnaspis aspidistrae), Planococcus spp., for example, Planococcus citri, Prosopidopsylla flava, Protopulvinaria pyriformis ), Pseudaulacaspis pentagona, Pseudococcus spp., For example, Pseudococcus calceolariae, Pseudococcus comstocki, Pseudococcus comstocki Pseudococcus longispinus, Pseudococcus maritimus, Pseudococcus viburni, Psyllopsis spp., Psylla spp., for example Listen, Psylla buxi, Psylla Marley (Psylla mali), Psylla pyri, Pteromalus spp., Pulvinaria spp., Pyrilla spp., Quadraspidiotus spp., For example, Quadraspidiotus juglansregiae, Quadraspidiotus ostreaeformis, Quadraspidiotus perniciosus, Quesada gigas ), Rastrococcus spp., Rhopalosiphum spp., For example, Rhopalosiphum maidis, Rhopalosiphum oxyacanthae, Rhopalosiphum Padi (Rhopalosiphum padi), Rhopalosiphum rufiabdominale, Saissetia spp., For example, Saissetia coffeae, Saissetia miranda, Saissetia neglecta, Saissetia oleae, Scaphoideus titanus, Schizaphis graminum, Selenaspeedus articulatus ( Selenaspidus articulatus), Sipha flava, Sitobion avenae, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Siphoninus Philileae (Sip honinus phillyreae), Tenalapara malayensis, Tetragonocephela spp., Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp ., For example, Toxoptera aurantii, Toxoptera citricidus, Trialeurodes vaporariorum, Trioza spp., For example , Trioza diospyri, Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp.;

From the suborder Heteroptera, for example Aelia spp., Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., for example, Cimex adjunctus, Cimex Cimex hemipterus, Cimex lectularius, Cimex pilosellus, Collaria spp., Creontiades dilutus, Dasynus piperis ), Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., For example, Euschistus heros ( Euschistus heros), Euschistus servus, Euschistus tristigmus, Euschistus variolarius, Eurydema spp., Eurygaster spp., Halyomorpha halys, Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptocorisa varicornis ), Leptoglosus occidentalis, Leptoglosus philopus (Leptoglo ssus phyllopus), Lygocoris spp., e.g., Lygocoris pabulinus, Lygus spp., e.g., Lygus elisus, Lygus hess Lygus hesperus, Lygus lineolaris, Macropes excavatus, Megacopta cribraria, Miridae, Monalonion atratum ), Nezara spp., For example, Nezara viridula, Nysius spp., Oebalus spp., Pentomidae, Fiesma Piesma quadrata, Piezodorus spp., For example, Piezodorus guildinii, Psallus spp., Pseudacysta persea, Rodnius ( Rhodnius) spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.;

From Hymenoptera, eg Acromyrmex spp., Athalia spp., eg Athalia rosae, Atta spp., Camponotus (Camponotus) spp., Dolichovespula spp., Diprion spp., for example Diprion similis, Hoplocampa spp., for example , Hoplocampa cookei, Hoplocampa testudinea, Lasius spp., Linepithema (Iridiomyrmex) humile , Monomorium pharaonis, Paratrechina spp., Paravespula spp., Plagiolepis spp., Sirex spp., for example , Sirex noctilio, Solenopsis invicta, Tapinoma spp., Technomyrmex albipes, Urocerus spp., Vespa ) spp., for example Vespa crabro, Wasmannia auropunctata, Xeris spp.;

from Isopoda, for example Armadillidium vulgare, Oniscus asellus, Porcellio scaber;

From Isoptera, for example Coptotermes spp., for example Coptotermes formosanus, Cornitermes cumulans, Cryptotermes ) spp., Incisitermes spp., Kalotermes spp., Microtermes obesi, Nasutitermes spp., Odontotermes spp., Porotermes spp., Reticulitermes spp., for example Reticulitermes flavipes, Reticulitermes hesperus;

From Lepidoptera, eg Achroia grisella, Acronicta major, Adoxophyes spp., eg Adoxophyes orana , Aedia leucomelas, Agrotis spp., for example Agrotis segetum, Agrotis ipsilon, Alabama spp., for example , Alabama argillacea, Amyelois transitella, Anarsia spp., Anticarsia spp., for example, Anticarsia gemmatalis (Anticarsia gemmatalis), Argyroploce spp., Autographa spp., Barathra brassicae, Blastodacna atra, Borbo cinnara, minor Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticula (Capua reticulana), Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp., for example, Kilo Chilo plejadellus, Chilo suppressalis, Choreutis pariana utis pariana), Choristoneura spp., Chrysodeixis chalcites, Clysia ambiguella, Cnaphalocerus spp., Cnaphalocerosis medi Cnaphalocrocis medinalis, Cnephasia spp., Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Cydia spp ., For example, Cydia nigricana, Cydia pomonella, Dalaca noctuides, Diaphania spp., Diparopsis spp ., Diatraea saccharalis, Dioryctria spp., for example Dioryctria zimmermani, Earias spp., Ecdytolopa au Ecdytolopha aurantium, Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp., e.g. Ephestia elutella, Ephesus Ephestia kuehniella, Epinotia spp., Epiphyas postvittana, Erannis spp., Erschoviella musculana, eti Etiella spp., Eudocima spp., Eulia spp., Eupoecilia a mbiguella), Euproctis spp., e.g., Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella ), Gracillaria spp., Grapholitha spp., such as Grapholita molesta, Grapholita prunivora, Hedylepta spp., Helicoverpa spp., e.g., Helicoverpa armigera, Helicoverpa zea, Heliothis spp., e.g., Heliotis vire sense (Heliothis virescens), Hepialus spp., for example, Hepialus humuli, Hofmannophila pseudospretella, Homoeosoma spp., Homona (Homona) spp., Hyponomeuta padella, Kakivoria flavofasciata, Lampides spp., Laphygma spp., Laspeiresia molesta (Laspeyresia molesta), Leucinodes orbonalis, Leucoptera spp., for example, Leucoptera coffeella, Lithocolletis spp., for example, Lithocolletis blancardella, Lithophane antennata, Lovesia (Lob esia) spp., e.g., Lobesia botrana, Loxagrotis albicosta, Lymantria spp., e.g., Lymantria dispar, Rio Lyonetia spp., for example, Lyonetia clerkella, Malacosoma neustria, Maruca testulalis, Mamestra brassicae ), Melanitis leda, Mocis spp., Monopis obviella, Mythimna separata, Nemapogon cloacellus, neem Nymphula spp., Oiketicus spp., Omphisa spp., Operophtera spp., Oria spp., Orthaga spp., Ost Ostrinia spp., for example Ostrinia nubilalis, Panolis flammea, Parnara spp., Pectinophora spp., for example , Pectinophora gossypiella, Perileucoptera spp., Phthorimaea spp., For example, Phthorimaea operculella, Philokni Phyllocnistis citrella, Phyllonorycter spp., for example Phyllonorycter blancardella, Phyllonorycter crataegella, Pieris spp., for example Pieris rapae, Platynota stultana, Plodia interfunctella interpunctella), Plusia spp., Plutella xylostella (= Plutella maculipennis), Podesia spp., for example, Podesia syringae (Podesia syringae), Prays spp., Prodenia spp., Protoparce spp., Pseudaletia spp., e.g., Pseudaletia unipuncta), Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., For example, Schoenobius Schoenobius bipunctifer, Scirpophaga spp., For example, Scirpophaga innotata, Scotia segetum, Sesamia spp., For example, Sesamia inferens, Sparganothis spp., Spodoptera spp., For example, Spodoptera eradiana, Spodoptera exi Gua (Spodoptera exigua), Spodoptera frugiperda, Spodoptera praefica, Startmopoda ( Stathmopoda) spp., Stenoma spp., Stomopteryx subsecivella, Synanthedon spp., Tecia solanivora, Thaumetopoea spp., Thermesia gemmatalis, Tinea cloacella, Tinea pellionella, Tineola bisselliella, Tortrix spp., Tree Trichophaga tapetzella, Trichoplusia spp., e.g. Trichoplusia ni, Tryphoryza incertulas, Tuta absoluta , Virachola spp.;

From Orthoptera or Saltatoria, for example Acheta domesticus, Dichroplus spp., Gryllotalpa spp., For example Grill Rotalpa gryllotalpa, Hieroglyphus spp., Locusta spp., for example Locusta migratoria, Melanoplus spp ., for example Melanoplus devastator, Paratlanticus ussuriensis, Schistocerca gregaria;

From Phthiraptera, for example Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloxera vastatrix ), Phthirus pubis, Trichodectes spp.;

from Psocoptera, for example Lepinotus spp., Liposcelis spp.;

From Siphonaptera, for example Ceratophyllus spp., Ctenocephalides spp., for example Ctenocephalides canis, Ctenocephalides felis ( Ctenocephalides felis), Pulex irritans, Tunga penetrans, Xenopsylla cheopis;

From Thysanoptera, for example Anaphothrips obscurus, Baliothrips biformis, Chaetanaphothrips leeuweni, Drepanothrips leu Terry (Drepanothrips reuteri), Enneothrips flavens, Frankliniella spp., For example, Frankliniella fusca, Frankliniella occidentalis ( Frankliniella occidentalis), Frankliniella schultzei, Frankliniella tritici, Frankliniella vaccinii, Frankliniella williamsi, Haplothrips spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus ), Scirtothrips spp., Taeniothrips cardamomi, Thrips spp., for example, Thrips palmi, Thrips tabasi (Thrips) tabaci);

Zygentoma (= Thysanura), for example Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus, Thermobia domestica (Thermobia domestica);

from Symphyla, eg Scutigerella spp., eg Scutigerella immaculata;

Pests from the phylum Mollusca, for example from Bivalvia, for example Dreissena spp.;

and from Gastropoda, for example Arion spp., for example Arion ater rufus, Biomphalaria spp., Bulinus spp., Deroseras ( Deroceras) spp., for example, Deroceras laeve, Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp. , Succinea spp.;

Plant pests from the phylum Nematoda, namely plant parasitic nematodes, in particular Aglenchus spp., for example Aglenchus agricola, Anguina spp., for example, Anguina tritici, Aphelenchoides spp., For example, Aphelenchoides arachidis, Aphelenchoides fragariae, Bellonolai Moose (Belonolaimus) spp., for example Belonolaimus gracilis, Belonolaimus longicaudatus, Belonolaimus nortoni, Bursaphelenchus spp., for example, Bursaphelenchus cocophilus, Bursaphelenchus eremus, Bursaphelenchus xylophilus, Cacopaurus spp., examples For example, Cacopaurus pestis, Criconemella spp., For example, Criconemella curvata, Criconemella onoensis, Criconemella orr Criconmella ornata, Criconemella rusium, Criconemella xenoplax (= Mesocriconema xenoplax), Criconemoides spp. , For example, Criconemoides perniae (Criconemoi des ferniae), Criconemoides onoense, Criconemoides ornatum, Ditylenchus spp., e.g., Ditylenchus dipsaci, Dolly Dolichodorus spp., Globodera spp., for example, Globodera pallida, Globodera rostochiensis, Helicotylenchus spp. , For example, Helicotylenchus dihystera, Hemicriconemoides spp., Hemicycliophora spp., Heterodera spp., For example, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Hirschmaniella spp., Hoplolaimus spp., Longidorus (Longidorus) spp., For example, Longidorus africanus, Meloidogyne spp., For example, Meloidogyne chitwoodi, Meloidogyne phalax ( Meloidogyne fallax), Meloidogyne hapla, Meloidogyne incognita, Meloidogyne incognita, Meloinema spp., Nacobbus spp., Neotylenchus spp. , Paralongidorus spp., Paraphele nchus) spp., Paratrichodorus spp., for example, Paratrichodorus minor, Paratylenchus spp., Pratylenchus spp., for example, Pratylenchus penetrans, Pseudohalenchus spp., Psilenchus spp., Punctodera spp., Quinisulcius spp., Radopolus (Radopholus) spp., for example, Radopholus citrophilus, Radopholus similis, Rotylenchulus spp., Rotylenchus spp. , Scutellonema spp., Subanguina spp., Trichodorus spp., for example, Trichodorus obtusus, Trichodorus primitivus , Tylenchorhynchus spp., for example, Tylenchorhynchus annulatus, Tylenchulus spp., for example, Tylenchulus semipenetrans, spp. Xiphinema spp., eg Xiphinema index.

Compounds of formula (I) optionally, at specific concentrations or application rates, also as herbicides, emollients, growth regulators or plant property improvers, fungicides or decontaminants, such as fungicides, antifungals, antibacterials, viricides (against viroids) agonists) or agonists against MLO (mycoplasma-like organisms) and RLO (rickettsia-like organisms). If appropriate, they can also be used for the synthesis of other active compounds. It can also be used as an intermediate or precursor for

Formulation/use form

The present invention also relates to preparations, in particular preparations for controlling unwanted pests. The formulation can be applied to pest animals and/or their habitat.

The formulations of the present invention may be provided to the end user in a "ready to use" use form, ie applied directly to the plant or seed via a suitable device, such as a sprayer or spreader. Alternatively, the formulation may be provided to the end user in the form of a concentrate which must be diluted with water, preferably immediately before use. Unless otherwise indicated, therefore, the term "formulation" refers to such a concentrate, while the term "use form" refers to a "ready-to-use" solution, ie generally to the end user as such a diluted preparation.

The formulations of the present invention can be prepared in a conventional manner, for example, by mixing a compound of the present invention with one or more suitable adjuvants, such as those disclosed herein.

The formulation comprises at least one compound of the present invention and at least one agriculturally suitable adjuvant such as carrier(s) and/or surfactant(s).

Carriers are generally inert solid or liquid, natural or synthetic, organic or inorganic substances. Carriers generally improve application of the compounds, for example to plants, plant parts or seeds. Examples of suitable solid carriers are ammonium salts, in particular ammonium sulfate, ammonium phosphate and ammonium nitrate, natural rock flours such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, silica gel and synthetic rock flours. , such as, but not limited to, finely divided silica, alumina and silicates. Examples of solid carriers typically useful for preparing granules include crushed and fractionated natural rocks such as calcite, marble, pumice, meerschaum and dolomite, synthetic granules of inorganic and organic flours and granules of organic materials such as paper, sawdust, coconut shells, corn cobs and tobacco stalks, but are not limited thereto. Examples of suitable liquid carriers include, but are not limited to, water, organic solvents, and combinations thereof. Examples of suitable solvents are, for example, aromatic and non-aromatic hydrocarbons (such as cyclohexane, paraffins, alkylbenzenes, xylenes, toluene, tetrahydronaphthalene, alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride ), alcohols and polyols (which may also be optionally substituted, etherified and/or esterified such as ethanol, propanol, butanol, benzylalcohol, cyclohexanol or glycols), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone or cyclohexanone), esters (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides (such as dimethylformamide or fatty acid amides) and their esters, lactams (such as N -alkylpyrrolidones, in particular N-methylpyrrolidone) and lactones, sulfones and sulfoxides (eg dimethyl sulfoxide), oils of plant or animal origin, nitriles (alkyl nitriles such as acetonitrile, propionotrile, butyronitrile) or aromatic nitriles such as benzonitrile), carbonic acid esters (cyclic carbonic acid esters such as ethylene carbonate, propylene carbonate, butylene carbonate, or dialkyl carbonic acid esters such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dioctyl carbonates), including polar and non-polar organic chemical liquids. The carrier may also be a liquefied gaseous extender, i.e. a liquid that is a gas under standard temperature and pressure, for example aerosol propellants such as halohydrocarbons, butanes, propane, nitrogen and carbon dioxide.

Preferred solid carriers are selected from clay, talc, and silica.

Preferred liquid carriers are selected from water, fatty acid amides and their esters, aromatic and non-aromatic hydrocarbons, ramtams, lactones, carbonic acid esters, ketones, (poly)ethers.

The amount of carrier typically ranges from 1 to 99.99%, preferably from 5 to 99.9%, more preferably from 10 to 99.5%, and most preferably from 20 to 99% by weight of the formulation.

The liquid carrier is typically present in the range of 20 to 90%, for example 30 to 80% by weight of the formulation.

Solid carriers are typically present in the range of 0 to 50%, preferably 5 to 45%, eg 10 to 30% by weight of the formulation.

When a formulation contains more than one carrier, the abridged range refers to the total amount of carriers.

Surfactants are ionic (cationic or anionic), amphoteric or nonionic surfactants such as ionic or nonionic emulsifier(s), foam former(s), dispersant(s), wetting agent(s), penetrating agent(s) enhancer(s) and any mixtures thereof. Examples of suitable surfactants are salts of polyacrylic acid, ethoxylated poly(alpha-substituted)acrylate derivatives, salts of lignosulfonic acid (such as sodium lignosulfonate), salts of phenolsulfonic acid or naphthalenesulfonic acid, alcohols, fatty acids or Polycondensates of ethylene oxide and/or propylene oxide with or without fatty amines (e.g. polyoxyethylene fatty acid esters such as castor oil ethoxylates, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers ), substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (preferably alkyl taurates), polyethoxylated alcohols or phosphoric acid esters of phenols, fatty esters of polyols (such as glycerol, fatty acid esters of sorbitol or sucrose), sulfates (such as alkyl sulfates and alkyl ether sulfates), sulfonates (such as alkylsulfonates, arylsulfonates and alkylbenzene sulfonates), sulfonates of naphthalene/formaldehyde oxidized polymers, phosphate esters, protein hydrolysates, lignosulfite waste liquors and methylcellulose. Any reference to salts in this context preferably means the respective alkali, alkaline earth and ammonium salts.

Preferred surfactants are ethoxylated poly(alpha-substituted)acrylate derivatives, polycondensates of ethylene oxide and/or propylene oxide with alcohols, polyoxyethylene fatty acid esters, alkylbenzene sulfonates, sulfonates of naphthalene/formaldehyde polyoxyethylene fatty acid esters such as castor oil ethoxylates, sodium lignosulfonates and arylphenol ethoxylates.

The amount of surfactant typically ranges from 5 to 40%, for example from 10 to 20% by weight of the formulation.

Further examples of suitable auxiliaries are water repellents, drying agents, binders (tackifiers, tackifiers, fixatives such as carboxymethylcellulose, natural and synthetic polymers in powder, granular or latex form such as gum arabic, polyvinyl alcohol and polyvinyl acetate). , natural phospholipids such as cephalin and lecithin and synthetic phospholipids, polyvinylpyrrolidone and tylose), thickeners and secondary thickeners (such as cellulose ethers, acrylic acid derivatives, xanthan gum, modified clays, for example available under the Bentone name). products, and finely divided silica), stabilizers (e.g. low temperature stabilizers, preservatives (e.g. dichlorophen, benzyl alcohol hemiformal, 1,2-benzisothiazolin-3-one, 2-methyl- 4-isothiazolin-3-one), antioxidants, light stabilizers, in particular UV stabilizers, or other agents to improve chemical and/or physical stability), dyes or pigments (such as inorganic pigments, e.g. iron oxides) , titanium oxide and Prussian blue; organic dyes such as alizarin, azo and metal phthalocyanine dyes), antifoaming agents (eg silicone antifoam and magnesium stearate), antifreeze agents, tackifiers, gibberellins and processing aids, minerals and vegetable oils, fragrances, waxes, nutrients (including trace nutrients such as salts of iron, magnesium, iron, copper, cobalt, molybdenum and zinc), protective colloids, thixotropic materials, penetrants, sequestering agents, and complexing agents.

The choice of adjuvant depends on the intended mode of application of the compound of the present invention and/or the physical properties of the compound(s). Furthermore, auxiliaries can be selected to impart specific properties (technical, physical and/or biological properties) to the preparation or to the use forms prepared therefrom. The choice of adjuvants may allow for customization of the formulation to specific needs.

The formulation comprises a pesticidally / acaricidal / nematicidally effective amount of the compound (s) according to the invention. The term "effective amount" means an amount sufficient to control harmful insects/mites/nematodes on cultivated plants or to protect materials and which does not cause substantial damage to the treated plants. This amount can vary within wide limits and depends on various factors such as the species of insect/mite/nematode to be controlled, the cultivated plant or material treated, the climatic conditions and the particular compound of the present invention used. In general, the formulations according to the present invention contain from 0.01% to 99% by weight, preferably from 0.05% to 98% by weight, more preferably from 0.1% to 95% by weight, even more preferably from 0.5% to 90% by weight, most preferably from 1% to 80% by weight of the compound of the present invention. It is possible for a formulation to contain two or more compounds of the present invention. In this case, the abridged range refers to the total amount of the compound of the present invention.

The formulations of the present invention may be formulated into any conventional formulation type, such as solutions (eg aqueous solutions), emulsions, water-based and oil-based suspensions, powders (eg wettable powders, soluble powders), dusts, pastes. , granules (eg soluble granules, granules for spreading), emulsified suspension concentrates, natural or synthetic products impregnated with the compounds of the present invention, fertilizers and also microcapsules in polymeric substances. The compounds of the present invention may exist in suspended, emulsified or dissolved form. Examples of certain suitable formulation types include solutions, aqueous concentrates (e.g. SL, LS), dispersible concentrates (DC), suspensions and suspension concentrates (e.g. SC, OD, OF, FS), Emulsifiable concentrates (eg EC), emulsions (eg EW, EO, ES, ME, SE), capsules (eg CS, ZC), pastes, pills, wettable powders or dusts (eg For example, WP, SP, WS, DP, DS), compacts (eg BR, TB, DT), granules (eg WG, SG, GR, FG, GG, MG), insecticidal articles ( eg LN), as well as plant propagation materials such as gel formulations for seed treatment (eg GW, GF). These and additional formulation types have been defined by the Food and Agriculture Organization of the United Nations (FAO). ["Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2nd, 6th. Ed., May 2008, Croplife International].

Preferably, the formulation of the present invention is in the form of one of the following types: EC, SC, FS, SE, OD, WG, WP, CS, more preferably EC, SC, OD, WG, CS.

Further details regarding formulation types and examples of their preparation are provided below. When more than one compound of the present invention is present, the abbreviated amount of the compound of the present invention refers to the total amount of the compound of the present invention. This also applies mutatis mutandis to any additional component of the formulation, if more than one representative of such component is present, for example a wetting agent or binder.

i) aqueous concentrates (SL, LS)

10-60% by weight of at least one compound of the present invention and 5-15% by weight of a surfactant (e.g. polycondensate of ethylene oxide and/or propylene oxide with an alcohol), so that the total amount is 100% by weight It is soluble in an amount of water and/or an aqueous solvent (eg an alcohol such as propylene glycol or a carbonate such as propylene carbonate). Prior to application, the concentrate is diluted with water.

ii) Dispersible Concentrate (DC)

5-25% by weight of at least one compound of the present invention and 1-10% by weight of a surfactant and/or binder (e.g. polyvinylpyrrolidone) in a total amount of 100% organic solvent (e.g. for example, cyclohexanone). Dilution with water gives a dispersion.

iii) emulsifiable concentrate (EC)

15-70% by weight of at least one compound of the present invention and 5-10% by weight of a surfactant (e.g., a mixture of calcium dodecylbenzenesulfonate and castor oil ethoxylate), so that the total amount is 100% by weight It is soluble in an amount of a water-insoluble organic solvent (eg an aromatic hydrocarbon or a fatty acid amide) and, if necessary, a further water-soluble solvent. Dilution with water gives an emulsion.

iv) Emulsion (EW, EO, ES)

5-40% by weight of at least one compound of the present invention and 1-10% by weight of a surfactant (e.g., a mixture of calcium dodecylbenzenesulfonate and castor oil ethoxylate, or without alcohol or with alcohol and ethylene oxides and/or polycondensates of propylene oxide) are soluble in 20-40% by weight of water-insoluble organic solvents (eg aromatic hydrocarbons). Using an emulsifying machine, this mixture is added to an amount of water bringing the total amount to 100%. The final formulation is a homogeneous emulsion. Prior to application, the emulsion may be further diluted with water.

v) Suspensions and suspension concentrates

v-1) water-based (SC, FS)

In suitable grinding equipment, such as an agitated ball mill, 20-60% by weight of at least one compound of the present invention is mixed with 2-10% by weight of a surfactant (e.g., sodium lignosulfonate and polyoxyethylene fatty alcohol). ether), 0.1-2% by weight of a thickener (eg xanthan gum) and water are added and milled to give a fine active substance suspension of the active compound. Water is added in such an amount that the total amount is 100% by weight. Dilution with water gives a stable suspension of the active substance. In the case of FS type formulations, up to 40% by weight of binder (eg polyvinyl alcohol) is added.

v-2) Oil-Based (OD, OF)

In a suitable grinding equipment mill, for example an agitated ball mill, 20-60% by weight of at least one compound according to the invention is mixed with 2-10% by weight of a surfactant (e.g. sodium lignosulfonate and polyoxyethylene fatty alcohol ether), 0.1-2% by weight of a thickener (eg modified clay, especially Bentone, or silica) and an organic carrier are added and ground to give a fine active substance oil suspension. The organic carrier is added in an amount to be 100% by weight of the total amount. Dilution with water gives stable dispersions of the active substance.

vi) water-dispersible granules and water-soluble granules (WG, SG)

1-90% by weight, preferably 20-80% by weight, most preferably 50-80% by weight of at least one compound of the present invention is a surfactant (e.g. sodium lignosulfonate and sodium alkylnaphthylsulfonate ) and potentially carrier materials are added, finely ground and converted into water-dispersible or water-soluble granules via typical technical equipment such as, for example, extrusion, spray drying, fluid bed granulation. Surfactant and carrier material are used in an amount such that the total amount is 100% by weight. Dilution with water gives stable dispersions or solutions of the active substance.

vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)

50-80% by weight of at least one compound of the present invention is combined with 1-20% by weight of a surfactant (eg sodium lignosulfonate, sodium alkylnaphthylsulfonate) and a total amount of 100% by weight It is milled in a rotor/stator mill with the addition of a solid carrier, eg silica gel. Dilution with water gives stable dispersions or solutions of the active substance.

viii) Gels (GW, GF)

In an agitated ball mill, 5-25% by weight of at least one compound of the present invention is 3-10% by weight of a surfactant (eg, sodium lignosulfonate), 1-5% by weight of a binder (eg, carboxymethylcellulose) and water in a total amount of 100% by weight are added and pulverized. This produces a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.

ix) Microemulsion (ME)

5-20% by weight of at least one compound of the present invention is 5-30% by weight of an organic solvent blend (eg fatty acid dimethylamide and cyclohexanone), 10-25% by weight of a surfactant blend (eg , polyoxyethylene fatty alcohol ether and arylphenol ethoxylate) and water in a total amount of 100% by weight. This mixture is stirred for 1 hour to spontaneously generate a thermodynamically stable microemulsion.

x) microcapsules (CS)

5-50% by weight of at least one compound of the present invention, 0-40% by weight of a water insoluble organic solvent (eg aromatic hydrocarbon), 2-15% by weight of an acrylic monomer (eg methyl methacrylate) , methacrylic acid and di- or triacrylate) is dispersed in an aqueous solution of a protective colloid (eg polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, 5-50% by weight of at least one compound of the present invention, 0-40% by weight of a water insoluble organic solvent (eg aromatic hydrocarbon), and an isocyanate monomer (eg diphenylmethane 4, 4'-diisocyanate) is dispersed in an aqueous solution of a protective colloid (eg polyvinyl alcohol), resulting in the formation of polyurea microcapsules. Optionally, also the addition of a polyamine (eg hexamethylenediamine) is used to effect the formation of polyurea microcapsules. The monomer is in an amount of 1-10% by weight of the total CS formulation.

xi) Dispersants (DP, DS)

1-10% by weight of at least one compound of the present invention is finely ground and intimately mixed with a solid carrier in an amount to give a total amount of 100% by weight, such as ground kaolin.

xii) granules (GR, FG)

0.5-30% by weight of at least one compound of the present invention is finely ground and associated with a solid carrier (eg silicate) in an amount up to a total amount of 100% by weight.

xiii) Ultra Low Volume Liquids (UL)

1-50% by weight of at least one compound of the present invention is dissolved in an amount of an organic solvent, such as an aromatic hydrocarbon, for a total amount of 100% by weight.

Formulation types i) to xiii) optionally comprise further auxiliaries such as 0.1-1% by weight of preservatives, 0.1-1% by weight of antifoaming agents, 0.1-1% by weight of dyes and/or pigments and 5-10% by weight of antifreeze agents. can do.

mixture

The compounds of formula (I) can thus also be used for one or more suitable killing agents, for example to broaden the range of action, prolong the duration of action, increase the rate of action, prevent repellency or prevent the development of resistance. To be applied as a mixture with fungicides, antimicrobials, acaricides, molluscicides, nematocides, insecticides, microbial agents, beneficial species, herbicides, fertilizers, algae repellents, biotonics, bactericides, emollients, infochemicals and/or plant growth regulators. can In addition, these active compound combinations can improve plant growth and/or tolerance to abiotic factors such as high or low temperatures, drought or elevated water content or soil salinity. It may also improve flowering and fruiting performance, optimize germination capacity and root development, promote harvest and improve yield, affect maturation, improve quality and/or nutritional value of the harvest, extend shelf life, and/or improve processability of the harvest. Do.

Furthermore, the compounds of formula (I) may be present in admixture with other active compounds or biochemicals such as attractants and/or algae repellents and/or plant activators and/or growth regulators and/or fertilizers. Similarly, the compounds of formula (I) can be used to improve plant properties such as, for example, growth, yield, and quality of the harvest.

In certain embodiments according to the present invention, the compounds of formula (I) are present in preparations or use forms prepared from these preparations in mixtures with further compounds, preferably those described below.

If one of the compounds mentioned below can occur in different tautomeric forms, these forms are also included, even if not explicitly stated in each case. In addition, all named mixing partners are optionally capable of forming salts with suitable bases or acids, provided that their functional groups allow this.

Insecticides/caricides/nematicides

The active compounds identified herein by their generic names are known and described, for example, in the Pesticide Handbook ("The Pesticide Manual" 16th Ed., British Crop Protection Council 2012) or on the Internet (eg http: http://www.alanwood.net/pesticides). The classification is based on the current IRAC Mechanism of Action classification system at the time of filing of this application.

(1) Acetylcholinesterase (AChE) inhibitors, preferably alanicab, aldicarb, bendiocarb, benfuracarb, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, ethi Offencarb, phenobucarb, formetanate, furatiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pyrimicarb, propoxur, thiodicarb, thiophanox, triaza carbamates selected from mate, trimetacarb, XMC and xylylcarb; or acephate, azametifos, azinphos-ethyl, azinphos-methyl, cadusaphos, chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, Methone-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfotone, EPN, ethion, etoprophos, palmpur, phenamiphos, fenitrothion, fenthion, phosthiazate, heptenophos, imisiaphos, isofenphos, isopropyl O-(methoxyaminothiophosphoryl) salicylate, isoxathione, malathion, mecarbam, metamidofos, methidathione, mebinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion-methyl, pentoate, phorate, fosalone, phosmet, phosphamidon, phoxim, pyrimiphos- Methyl, Profenophos, Profetamphos, Prothiophos, Pyraclophos, Pyridafenthione, Quinalphos, Sulfhotep, Tebupirimphos, Temephos, Tabufos, Tetrachlorvinphos, Thiometone, Triazo An organophosphate selected from phos, trichlorphon and bamidothion.

(2) GABA-gated chloride channel blockers, preferably cyclodiene-organochlorine selected from chlordane and endosulfan or phenylpyrazole selected from ethiprole and fipronil (fiprol).

(3) sodium channel modulators, preferably acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin s-cyclopentenyl isomer, bioresmet Lin, cycloprothrin, cyfluthrin, beta-cypermethrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta- Cypermethrin, Zeta-Cypermethrin, Cyphenothrine [(1R)-trans isomer], Deltamethrin, Emfenthrin [(EZ)-(1R) isomer], Espenvalerate, Etopenprox, Fenpropart Lin, Fenvalerate, Flucitrinate, Flumethrin, Tau-Fluvalinate, Halfenprox, Imiprothrin, Cadethrin, Momfluorothrin, Permethrin, Phenothrin [(1R)-trans isomer], pralethrin, pyrethrins (pyrethrum), resmethrin, cilafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomer)], tralomethrin and transfluthrin or DDT or a pyrethroid selected from methoxychlor.

(4) nicotinic acetylcholine receptor (nAChR) competitive modulators, neonicotinoids, preferably selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam, or nicotine, or a sulfoximine selected from sulfoxaflor, or a butenolide selected from flupyradipuron, or a mesoionics selected from triflumezopyrim.

(5) a nicotinic acetylcholine receptor (nAChR) allosteric modulator (site I), spinosyn, preferably selected from spinetoram and spinosad.

(6) A glutamate-gated chloride channel (GluCl) allosteric modulator, preferably an avermectin/milbemycin selected from abamectin, emamectin benzoate, lepimectin and milbemectin.

(7) Juvenile hormone mimics, preferably juvenile hormone analogues selected from hydroprene, kinoprene and methoprene or phenoxycarb or pyriproxyfen.

(8) other non-specific (multisite) inhibitors, preferably alkyl halides selected from methyl bromide and other alkyl halides, or selected from chloropicrin or sulfuryl fluoride or borax or tartar emetics or diazomet and metam methyl isocyanate generator.

(9) Phenomenon TRPV channel modulators, preferably pyridine azomethane selected from pymetrozine and pyrifluquinazone, or pyropene selected from afidopyropen.

(10) A mite growth inhibitor affecting CHS1 selected from Clopentezine, Hexythiazox, Diflovidazin and Etoxazole.

(11) Bacillus thuringiensis subspecies Israelensis ( israelensis ), Bacillus sphaericus ( Bacillus sphaericus ), Bacillus thuringiensis subspecies Aizawai, Bacillus thuringiensis ( Bacillus thuringiensis ) Microbial disruptors of insect intestinal membranes selected from subspecies kurstaki , Bacillus thuringiensis subspecies tenebrionis , and Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab , a Bt plant protein selected from Cry3Bb and Cry34Ab1/35Ab1.

(12) an inhibitor of mitochondrial ATP synthase, preferably an ATP disruptor selected from diafenthiuron or an organotin selected from azocyclotin, cyhexatin and fenbutatin oxide, or propargite or tetradifone compound.

(13) Uncoupler of oxidative phosphorylation through disruption of the proton gradient selected from chlorfenapyr, DNOC and sulfluramide.

(14) A nicotinic acetylcholine receptor channel blocker selected from bensultap, cartap hydrochloride, thiocyram, and thiosultap-sodium.

(15) chitin biosynthesis inhibitors affecting CHS1, preferably bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, nobiflu A benzoylurea selected from muron, teflubenzuron and triflumuron.

(16) A chitin biosynthesis inhibitor, type 1, selected from buprofezin.

(17) A molting disruptor selected from cyromazines (particularly twin flies, i.e. flies).

(18) Ecdysone receptor agonists, diacylhydrazines, preferably selected from clomafenozide, halofenozide, methoxyfenozide and tebufenozide.

(19) An octopamine receptor agonist selected from amitraz.

(20) A mitochondrial complex III electron transport inhibitor selected from hydramethylnon, acequinocyl, fluacrypyrim and biphenazate.

(21) Mitochondrial complex I electron transport inhibitors, preferably METI acaricides and insecticides selected from fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad, or rotenone (Derris).

(22) Voltage-dependent sodium channel blockers, preferably oxadiazine selected from indoxacarb or semicarbazone selected from metaflumizone.

(23) Inhibitors of acetyl-CoA carboxylase, preferably tetronic acid and tetramic acid derivatives selected from spirodiclofen, spiromesifen, spiropidione and spirotetramat.

(24) A mitochondrial complex IV electron transport inhibitor, preferably a phosphide selected from aluminum phosphide, calcium phosphide, phosphine and zinc phosphide, or a cyanide selected from calcium cyanide, potassium cyanide and sodium cyanide.

(25) A mitochondrial complex II electron transport inhibitor, preferably a beta-ketonitrile derivative selected from cyenopyrafen and cyflumetofen, or a carboxanilide selected from fiflubamide.

(28) A ryanodine receptor modulator, preferably a diamide selected from chlorantraniliprole, cyanthraniliprole, cyclaniliprole, flubendiamide and tetraniliprole.

(29) A chordal organ modulator selected from flonicamide (with unspecified target site).

(30) GABA-gated chloride channel allosteric modulators, preferably meta-diamide selected from broflanilide or isoxazole selected from fluxamethamide.

(31) Baculovirus, preferably a granulosa virus (GV) selected from Cydia pomonella GV and Thaumatotibia leucotreta (GV) or Anticarsia gemmatalis gemmatalis ) MNPV and Helicoverpa armigera NPV.

(32) Nicotinic acetylcholine receptor allosteric modulators selected from GS-omega/kappa-HXTX-Hv1a peptides (site II).

(33) Acinonapyr, Afoxolaner, Azadirachtin, Benclotiaz, Benzoximate, Benzpyrimoxane, Bromopropylate, Chinomethionat, Chloropralethrin, Cryolite, Cyclobutriple Luram or Cyclobutrifen (CAS 1460292-16-3), Cycloxapride, Sietpyrafen, Cyhalodiamide, Dichloromezothiaz, Dicofol, Dimpropyridaz, Epsilon-Metofluthrin, Epsilon -momfluthrin, flomethoquine, fluazaindolizine, fluenesulfone, flufenerim, flufenoxystrobin, flupiprole, fluhexaphone, fluopyram, flupyrimine, fluralanor, fufenozide, Pufenthiophenox (CAS 1472050-04-6), guadipyr, heptafluthrin, imidaclotiz, iprodione, isocycloceram, kappa-bifenthrin, kappa-tefluthrin, rotilaner, meferfluthrin , oxazosulfil, pichonding, pyridalil, pyrifluquinazone, pyriminostrobin, sarolaner, spirobudiclofen, tetramethylfluthrin, tetrachlorantraniliprole, tigolaner, thioxazafen , thiofluoximate, ticlopyrazoflor, iodomethane, triflupentoxide (CAS 1472050-04-6); Further preparations based on Bacillus firmus (I-1582, Votivo) and azadirachtin (BioNeem), and also the following compounds: 1-{2-fluoro-4-methyl-5-[(2 ,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known from WO2006/043635) (CAS 885026- 50-6), 2-chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]piperidin-4-yl}- 4-(trifluoromethyl)phenyl]isonicotinamide (published in WO2006/003494) (CAS 872999-66-1), 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8 -methoxy-1,8-diazaspiro[4.5]dec-3-en-2-one (known from WO 2010052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethyl Phenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from EP 2647626) (CAS 1440516-42-6), PF1364 ( published in JP2010/018586) (CAS 1204776-60-2), (3E)-3-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-1,1,1 -Trifluoro-propan-2-one (published in WO2013/144213) (CAS 1461743-15-6), N-[3-(benzylcarbamoyl)-4-chlorophenyl]-1-methyl-3-( Pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (published from WO2010/051926) (CAS 1226889-14-0), 5-bromo-4-chloro- N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known as CN103232431) (CAS 1449220- 44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis -1-oxido-3-thietanyl)benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(triple Luoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxido-3-thietanyl)benzamide and 4-[(5S)-5-(3,5-dichlorophenyl )-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)benzamide (WO 2013/ 050317 A1) (CAS 1332628-83-7), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3, 3,3-Trifluoropropyl)sulfinyl]propanamide, (+)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3 -[(3,3,3-trifluoropropyl)sulfinyl]propanamide and (-)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]- N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propanamide (known from WO 2013/162715 A2, WO 2013/162716 A2, US 2014/0213448 A1) (CAS 1477923-37 -7), 5-[[(2E)-3-chloro-2-propen-1-yl]amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4- [(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile (known from CN 101337937 A) (CAS 1105672-77-2), 3-bromo-N-[4-chloro-2- Methyl-6-[(methylamino)thioxomethyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide, (Liudaibanzaxiannan, CN 103109816 A known) (CAS 1232543-85-9); N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy) -1H-pyrazole-5-carboxamide (known from WO 2012/034403 A1) (CAS 1268277-22-0), N-[2-(5-amino-1,3,4-thiadiazole-2 -yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (published in WO 2011/085575 A1) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3-dichloro-2-propen-1-yl)oxy]phenoxy]propoxy]-2 -methoxy-6-(trifluoromethyl)pyrimidine (known from CN 101337940 A) (CAS 1108184-52-6); (2E)- and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy )phenyl]hydrazinecarboxamide (known from CN 101715774 A) (CAS 1232543-85-9); 3-(2,2-dichloroethenyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenyl cyclopropanecarboxylic acid ester (known from CN 103524422 A) (CAS 1542271-46 -4); methyl (4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]indeno[1, 2-e][1,3,4]oxadiazine-4a(3H)-carboxylic acid methyl ester (known from CN 102391261 A) (CAS 1370358-69-2); 6-deoxy-3-O-ethyl-2,4-di-O-methyl-1-[N-[4-[1-[4-(1,1,2,2,2-pentafluoro Toxy)phenyl]-1H-1,2,4-triazol-3-yl]phenyl]carbamate]-α-L-mannopyranose (known from US 2014/0275503 A1) (CAS 1181213-14-8) ; 8-(2-Cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1] Octane (CAS 1253850-56-4), (8-anti)-8-(2-cyclopropylmethoxy-4-trifluoromethylphenoxy)-3-(6-trifluoromethylpyridazine-3- yl)-3-azabicyclo[3.2.1]octane (CAS 933798-27-7), (8-syn)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)- 3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (known from WO 2007040280 A1, WO 2007040282 A1) (CAS 934001-66-8), N-[4-(aminothioxomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1 H - Pyrazole-5-carboxamide (from CN 103265527 A) (CAS 1452877-50-7), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8 -diazaspiro[4.5]decane-2,4-dione (published in WO 2014/187846 A1) CAS 638765-58-8), ethyl 3-(4-chloro-2,6-dimethylphenyl)-8-methyl Toxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl-carboxylic acid ethyl ester (WO 2010/066780 A1, WO 2011151146 A1) (CAS 229023-00 -0), N- [1-(2,6-difluorophenyl)-1 H -pyrazol-3-yl]-2-(trifluoromethyl)benzamide (known from WO 2014/053450 A1) (CAS 1594624-87-9), N- [2-(2,6-difluorophenyl)-2 H -1,2,3-triazol-4-yl]-2-(trifluoromethyl) Benzamide (known from WO 014/053450 A1) (CAS 1594637-65-6), N-[1-(3,5-difluoro-2-pyridinyl)-1H-pyrazol-3-yl]- 2-(trifluoromethyl)benzamide (known from WO 014/053450 A1) (CAS 1594626-19-3).

fungicide

The active ingredients specified herein by their generic names are known and described, for example, in [The Pesticide Manual (16th Ed.British Crop Protection Council)] or on the Internet (eg www.alanwood.net/pesticides). can be searched in

All named fungicidal mixing partners of classes (1) to (15) can optionally form salts with suitable bases or acids, provided their functional groups allow this. All named mixing partners of classes (1) to (15) may include tautomeric forms, where applicable.

1) Inhibitors of ergosterol biosynthesis, for example (1.001) ciproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropidine, (1.006) pen Profimorph, (1.007) Fenpyrazamine, (1.008) Fluquinconazole, (1.009) Flutriafol, (1.010) Imazalil, (1.011) Imazalil Sulfate, (1.012) Ipconazole, (1.013) ( 1.020) Spiroxamine, (1.021) Tebuconazole, (1.022) Tetraconazole, (1.023) Triadimenol, (1.024) Tridemorph (1.025) Triticonazole, (1.026) (1R,2S,5S) -5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.027) (1S, 2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.028 ) (2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butane -2-ol, (1.029) (2R)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-tria Zol-1-yl)butan-2-ol, (1.030) (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1, 2,4-triazol-1-yl)propan-2-ol, (1.031) (2S)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]- 1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.032) (2S)-2-(1-chlorocyclopropyl)-4-[(1S)-2, 2-Dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.033) (2S)-2-[4-(4-chloro Phenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.034) (R)-[3-( 4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.035) (S) -[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, ( 1.036) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol; (1.037) 1-({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)- 1H-1,2,4-triazole, (1.038) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3 -dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.039) 1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl) oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.040) 1-{[rel(2R,3R)-3-(2-chlorophenyl) -2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.041) 1-{[rel( 2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl Thiocyanate, (1.042) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2, 4-dihydro-3H-1,2,4-triazole-3-thione, (1.043) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy- 2,6,6-Trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.044) 2-[(2R,4S,5R)- 1-(2,4-dichlorophenyl)-5-hydroxyl-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3- Thione, (1.045) 2-[(2R,4S,5S)-1-(2,4-dichlorophenyl)-5 -Hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.046) 2-[(2S,4R ,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-tria sol-3-thione, (1.047) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]- 2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.048) 2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy Roxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2S,4S,5S )-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole- 3-thione, (1.050) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1 ,2,4-triazole-3-thione, (1.051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazole- 1-yl)propan-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl) Butan-2-ol, (1.053) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl )butan-2-ol, (1.054) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazole-1- yl)pentan-2-ol, (1.055) mefentrifluconazole, (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl] methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2- (2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.058) 2-{[rel (2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluoro Phenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloro Methyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.060) 5-(allylsulfanyl)-1-{[3-(2- Chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-(allylsulfanyl)-1- {[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole , (1.062) 5-(allylsulfanyl)-1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl ]methyl}-1H-1,2,4-triazole, (1.063) N'-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl ]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.064) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy) Phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.065) N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoro Propoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.066) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl] Sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.067) N'-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl) Sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.068) N'-(2,5-dimethyl-4-{3-[(2,2,2-trifluoroethyl )sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.069) N'-(2,5-dimethyl-4-{3-[(2,2,3,3-tetra Fluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.070) N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)sul panyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.071) N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide, (1.072 ) N'-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.073) N'-(4 -{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.074) N'-[5-bromo-6 -(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimidoformamide, (1.075) N'-{4-[ (4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide, (1.076) N'-{5-bromide Mo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.077) N '-{5-Bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoform Amide, (1.078) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide , (1.079) N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.080) N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoform Amide, (1.081) Ippentrifluconazole, (1.082) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazole- 1-yl)propan-2-ol, (1.083) 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4 -triazol-1-yl)propan-2-ol, (1.084) 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1, 2,4-triazol-1-yl)propan-2-ol, (1.085) 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2- Hydroxy-propyl]imidazole-4-carbonitrile and (1.086) 4-[[6-[rac-(2R)-2-(2,4-difluorophenyl)-1,1- Difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile.

2) Inhibitors of the respiratory chain in complex I or II, for example (2.001) benzobindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxine, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapiroxad, (2.008) furametpyr, (2.009) isopetamide, (2.010) isopyrazam (anti-epimer enantiomer 1R,4S,9S), (2.011) iso Pyrazam (anti-epimer enantiomer 1S,4R,9R), (2.012) isopyrazam (anti-epimer racemic 1RS,4SR,9SR), (2.013) isopyrazam (syn-epimer racemate 1RS, 4SR, 9RS and a mixture of anti-epimer racemics 1RS, 4SR, 9SR), (2.014) isopyrazam (syn-epimer enantiomer 1R, 4S, 9R), (2.015) isopyrazam (syn- Epimer enantiomer 1S,4R,9S), (2.016) isopyrazam (syn-epimer racemic 1RS,4SR,9RS), (2.017) penflufen, (2.018) penthiopyrad, (2.019) PD Flumetofen, (2.020) Pyraziflumid, (2.021) Sedakic acid, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-indene-4 -yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-indene- 4-yl]-1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-indene -4-yl] -1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3- (trifluoromethyl) -N- [2'- (trifluoromethyl) biphenyl-2- yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H -inden-4-yl)benzamide, (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-indene-4- yl) -1H-pyrazole-4-carboxamide, (2. 028) Inpyrfluxam, (2.029) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-indene-4- yl]-1H-pyrazole-4-carboxamide, (2.030) fluindapyr, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3 -trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N-[( 3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine; (2.034) N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxyl Mead, (2.035) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4- Carboxamide, (2.036) N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxa Mead, (2.037) N-(5-chloro-2-ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxyl Mead, (2.038) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carb Boxamide, (2.039) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(dichloromethylene)-1 Fluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro- 1,4-Methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041) N-[1-(2,4- Dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H- Pyrazole-4-carboxamide, (2.042) N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -Methyl-1H-pyrazole-4-carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoro Romethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl- 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.045) N-cyclopropyl-3-(difluoromethyl)-5-fluoro -1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1H-pyrazole-4-carboxamide, (2.046) N-cyclopropyl-3-(difluoromethyl) -5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3-(difluoro Methyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.048) N-cyclopropyl-3-(difluoro Romethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carbothioamide, (2.049) N-cyclopropyl-3-(difluoromethyl )-5-Fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3-(difluoromethyl)-5 -Fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3-(difluoromethyl) -N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3-(difluoro Methyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-cyclopropyl-3-(difluoro Romethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-cyclopropyl-N-(2- Cyclopropyl-5-fluorobenzyl)-3 -(Difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055) N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)- 3-(Difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-( Difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057) pyrapropoin.

3) Inhibitors of the respiratory chain in complex III, for example (3.001) amethoctradine, (3.002) amulbromine, (3.003) oxacitrobin, (3.004) comethoxystrobin, (3.005) cumoxystrobin, (3.006) cyazopamide, (3.007) dimoxystrobin, (3.008) ethoxastrobin, (3.009) pamoxadone, (3.010) phenamidon, (3.011) fluphenoxystrobin, (3.012) fluoxastrobin , (3.013) cresoxim-methyl, (3.014) methominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrametostrobin, (3.019) Pyraoxystrobin, (3.020) Trifloxystrobin, (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2 -phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide, (3.022) (2E,3Z)-5-{[1- (4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.023) (2R)-2-{2 -[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.024) (2S)-2-{2-[(2,5-dimethylphenoxy) methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025) fenpicoxamide, (3.026) mandesstrobin, (3.027) N-(3-ethyl-3,5,5-trimethylcyclo Hexyl)-3-formamido-2-hydroxybenzamide, (3.028) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazole-3- yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029) methyl {5-[3-(2,4-dimethylphenyl)-1H-pyrazole-1 -yl]-2-methylbenzyl}carbamate, (3.030) methyltetraprole, (3.031) florylpicoxamide.

4) mitotic and cell division inhibitors such as (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thia Bendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine, (4.010 ) 3-chloro-5- (4-chlorophenyl) -4- (2,6-difluorophenyl) -6-methylpyridazine, (4.011) 3-chloro-5- (6-chloropyridine-3- yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4-(2-bromo-4-fluorophenyl)-N-(2,6-di Fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluoro Phenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.014) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3- Dimethyl-1H-pyrazol-5-amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H -Pyrazol-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.018) 4-(2 -Chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.019) 4-(2-chloro-4- Fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl) -N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl) )-1,3-dimethyl-1H-pyrazol-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.023) N-(2 -Bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.024) N-(2-bromo Phenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.025) N-(4-chloro-2,6-difluorophenyl )-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine.

5) Compounds capable of having multisite action, for example (5.001) Bordeaux mixture, (5.002) captapol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthe nate, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper (2+) sulfate, (5.010) dithianon, (5.011) dodin, (5.012) polpet, (5.013) mancozeb, ( 5.014) maneb, (5.015) metiram, (5.016) metiram zinc, (5.017) auxin-copper, (5.018) propineb, (5.019) sulfur and sulfur preparations including calcium polysulfide, (5.020) thiram, (5.021) Zineb, (5.022) Ziram, (5.023) 6-Ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3',4':5,6][1,4 ] dithino[2,3-c][1,2]thiazole-3-carbonitrile.

6) Compounds capable of inducing host defenses, eg (6.001) acibenzoral-S-methyl, (6.002) isothianil, (6.003) probenazole, (6.004) thiadinil.

7) amino acid and/or protein biosynthesis inhibitors such as (7.001) ciprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimeta Nyl, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline.

8) Inhibitors of ATP production, eg (8.001) Silthiofam.

9) Inhibitors of cell wall synthesis, for example (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamide, (9.006) pyrimorph, (9.007) varifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholine -4-yl) prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-( Morpholin-4-yl)prop-2-en-1-one.

10) Inhibitors of lipid and membrane synthesis, eg (10.001) propamocarb, (10.002) propamocarb-hydrochloride, (10.003) tolclofos-methyl.

11) Inhibitors of melanin biosynthesis, for example (11.001) tricyclazole, (11.002) 2,2,2-trifluoroethyl {3-methyl-1-[(4-methylbenzoyl)amino]butane-2- one} carbamate.

12) Inhibitors of nucleic acid synthesis, for example (12.001) benalaxyl, (12.002) benalaxyl-M (chiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).

13) Inhibitors of signal transduction, for example (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazide, (13.005) quinoxyfen, (13.006) vinclon sleepy.

14) Compounds that can act as uncouplers, eg (14.001) fluazinam, (14.002) meptyldinocap.

15) a further fungicide selected from the group consisting of: (15.001) Abcisic acid, (15.002) Benthiazole, (15.003) Betoxazine, (15.004) Capsimycin, (15.005) Carvone, (15.006) Chinomethiona (15.007) cupraneb, (15.008) ciflufenavid, (15.009) simoxanil, (15.010) ciprosulfamide, (15.011) flutianil, (15.012) fosetyl-aluminum, (15.013) fosse Tyl-Calcium, (15.014) Fosetyl-Sodium, (15.015) Methyl Isothiocyanate, (15.016) Metraphenone, (15.017) Mildiomycin, (15.018) Natamycin, (15.019) Nickel Dimethyldithiocarbamate , (15.020) nitrothal-isopropyl, (15.021) oxamocarb, (15.022) oxathiapiproline, (15.023) oxypentyin, (15.024) pentachlorophenol and salts, (15.025) phosphoric acid and salts thereof, ( 15.026) propamocarb-fosetylate, (15.027) pyriophenone (clazaphenone), (15.028) tebufloquine, (15.029) teclophthalam, (15.030) tolniphanide, (15.031) 1-( 4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazole-2 -yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.032) 1-(4-{4 -[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}py Peridin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.033) 2-(6-benzylpyridin-2-yl )quinazoline, (15.034) dipimetitron, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5- [2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)p Peridin-1-yl]ethanone, (15.036) 2-[3,5-bis(difluoro Romethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4, 5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.037) 2-[3,5-bis (Difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl ]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.038) 2-[6 -(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.039) 2-{(5R)-3-[2-(1-{[3,5- Bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2 -Oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.040) 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H -Pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}- 3-Chlorophenyl methanesulfonate, (15.041) Ipflufenoquin, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propane -2-ol, (15.043) fluoxafiproline, (15.044) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl] acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate, (15.045) 2 -Phenylphenol and salts thereof, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.047) quinofumeline , (15.048) 4-amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidin-2 (1H) -one), (15.049) 4-oxo-4 -[(2-phenylethyl)amino]butanoic acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N'-phenyl-N'-( Prop-2-yn-1-yl)thiophene-2-sulfo Nohydrazide, (15.052) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine, (15.053) 5-fluoro-2-[(4-methylbenzyl)oxy] Pyrimidin-4-amine, (15.054) 9-fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazepine, (15.055) but -3-yn-1-yl {6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl} Carbamate, (15.056) ethyl (2Z)-3-amino-2-cyano-3-phenylacrylate, (15.057) phenazine-1-carboxylic acid, (15.058) propyl 3,4,5-trihydride Roxybenzoate, (15.059) quinolin-8-ol, (15.060) quinolin-8-ol sulfate (2:1), (15.061) tert-butyl {6-[({[(1-methyl-1H-tetra zol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl )sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, (15.063) aminopyrphene, (15.064) (N'-[2-chloro-4-(2-fluorophenoxy) -5-methylphenyl] -N-ethyl-N-methylimidoformamide), (15.065) (N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylimido -formamide), (15.066) (2-{2-[(7,8-difluoro-2-methylquinolin-3-yl)oxy]-6-fluorophenyl}propan-2-ol), ( 15.067) (5-Bromo-1-(5,6-dimethylpyridin-3-yl)-3,3-dimethyl-3,4-dihydroisoquinoline), (15.068) (3-(4,4- difluoro-5,5-dimethyl-4,5-dihydrothieno[2,3-c]pyridin-7-yl)quinoline), (15.069) (1-(4,5-dimethyl-1H-benzyl) Midazol-1-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline), (15.070) 8-fluoro-3-(5-fluoro-3, 3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinolone, (15.071) 8-fluoro-3-(5-fluoro-3,3,4,4-tetramethyl-3,4- Dihydroisoquinolin-1-yl)quinolone, (15.072) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-8-fluoroquinoline , (15.073) (N-methyl-N-phenyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide), (15.074) (methyl {4 -[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}carbamate), (15.075) (N-{4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl]benzyl}-cyclopropane-carboxamide), (15.076) N-methyl-4-(5-(trifluoromethyl)-1,2,4- Oxadiazol-3-yl]benzamide, (15.077) N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3 -yl]benzamide, (15.078) N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide , (15.079) N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-cyclopropane-carboxamide, (15.080) N-(2 -Fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.081) 2,2-difluoro-N-methyl- 2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, (15.082) N-allyl-N-[[4-[5 -(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]acetamide, (15.083) N-[(E)-N-methoxy-C-methyl-carb Bonimidoyl]-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.084) N-[(Z)-N-methoxy-C -Methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.085) N-allyl-N-[[4 -[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-methyl]-propanamide, (15.086) 4,4-dimethyl-1-[[4-[ 5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-pyrrolidin-2-one, (15.087) N-methyl- 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-benzenecarbothioamide, (15.088) 5-methyl-1-[[4-[5-( Trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.089) N-((2,3-difluoro-4-[ 5-(Trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3,3-trifluoro-propanamide, (15.090) 1-methoxy-1 -methyl-3-[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.091) 1,1-diethyl-3 -[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.092) N-[[4-[5-(trifluoro) Romethyl)-1,2,4-oxadiazol-3-yl]phen-yl]methyl]propanamide, (15.093) N-methoxy-N-[[4-[5-(trifluoromethyl) -1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, (15.094) 1-methoxy-3-methyl-1-[[4-[5-(trifluoro Methyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.095) N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2 ,4-oxadiazol-3-yl]phenyl]-methyl)-cyclopropane-carboxamide, (15.096) N,2-dimethoxy-N-[[4-[5-(trifluoromethyl}- 1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.097) N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1, 2,4-oxadiazol-3-yl)phenyl]methyl]propanamide, (15.098) 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2 ,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.099) 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxa Diazol-3-yl]phenyl]methyl]urea, (15.100) 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole -3-yl]phenyl]methyl]urea, (15.101) 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperi Din-2-one, (15.10 2) 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one , (15.103) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3 -one, (15.104) 3,3-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidine- 2-one, (15.105) 1-[[3-fluoro-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]azepan-2 -one, (15.106) 4,4-dimethyl-2-[[4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidine -3-one, (15.107) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxa Zolidin-3-one, (15.108) ethyl (1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-pyrazol-4 -yl)acetate, (15.109) N,N-dimethyl-1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-1, 2,4-triazol-3-amine and (15.110) N-{2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl ]benzyl}butanamide.

Biological Pesticide as Mixing Component

Compounds of formula (I) can be combined with biological pesticides.

Biological pesticides include, inter alia, bacteria, fungi, yeasts, plant extracts and these products formed by microorganisms including proteins and secondary metabolites.

Biological agrochemicals include bacteria such as spore-forming bacteria, root-colonizing bacteria and bacteria that act as biological insecticides, fungicides or nematicides.

Examples of such bacteria that can be applied or used as biological pesticides are:

Bacillus amyloliquefaciens , strain FZB42 (DSM 231179), or Bacillus cereus , especially b. Cereus ( B. cereus ) strain CNCM I-1562 or Bacillus firmus ( Bacillus firmus ), strain I-1582 (registration number CNCM I-1582) or Bacillus pumilus ( Bacillus pumilus ), in particular strain GB34 (registration number ATCC 700814 ) and strain QST2808 (registration number NRRL B-30087), or Bacillus subtilis ( Bacillus subtilis ), in particular strain GB03 (registration number ATCC SD-1397), or Bacillus subtilis strain QST713 (registration number NRRL B-21661) or Bacillus subtilis ( Bacillus subtilis ) Strain OST 30002 (registration number NRRL B-50421), Bacillus thuringiensis , in particular B. Thuringiensis ( B. thuringiensis ) Subspecies israelensis (serotype H-14), strain AM65-52 (registration number ATCC 1276), or B. Thuringiensis ( B. thuringiensis ) subsp. aizawai , in particular strain ABTS-1857 (SD-1372), or b. Thuringiensis ( B. thuringiensis ) subsp. Kurstaki strain HD-1, or b. Thuringiensis ( B. thuringiensis ) subsp. Tenebrionis strain NB 176 (SD-5428), Pasteuria penetrans , Pasteuria spp . (Rotylenchulus reniformis nematode)-PR3 (registration number ATCC SD-5834), Streptomyces microflavus strain AQ6121 (= QRD 31.013, NRRL B-50550), Streptomyces Galbus ( Streptomyces galbus ) strain AQ 6047 (registration number NRRL 30232).

Examples of fungi and yeasts that can be applied or used as biological pesticides are:

Beauveria bassiana , in particular strain ATCC 74040, Coniothyrium minitans , in particular strain CON/M/91-8 (registration number DSM-9660), Lecanicillium spp. , in particular strain HRO LEC 12, Lecanicillium lecanii (previously known as Verticillium lecanii ), in particular strain KV01, Metarhizium anisopliae , in particular Strain F52 (DSM3884/ ATCC 90448), Metschnikowia fructicola , in particular strain NRRL Y-30752, Paecilomyces fumosoroseus (Current: Isaria fumosorosea ( Isaria fumosorosea )), in particular strain IFPC 200613, or strain Apopka 97 (registration number ATCC 20874), Paecilomyces lilacinus ), especially P. P. lilacinus strain 251 (AGAL 89/030550), Talaromyces flavus , in particular strain V117b, Trichoderma atroviride , in particular strain SC1 (registration number CBS 122089 ), Trichoderma harzianum , especially T. Harzianum rifai ( T. harzianum rifai ) T39 (registration number CNCM I-952).

Examples of viruses that can be applied or used as biological pesticides are:

Adoxophyes orana (summer fruit leaf roll) granulosis virus (GV), Cydia pomonella ( Cydia pomonella ) (codling moth) granulosis virus (GV), Helicoverpa armigera ) (cotton worm) nuclear polyhedron virus (NPV), Spodoptera exigua ( Spodoptera exigua ) mNPV, Spodoptera frugiperda (Autumn armyworm) mNPV, Spodoptera littoralis ( Spodoptera littoralis ) (African cotton leaf beetle) NPV.

Also included are bacteria and fungi that are added as 'inoculum' to plants or plant parts or plant organs and that, by their specific properties, promote plant growth and plant health. Examples that may be mentioned are:

Agrobacterium ( Agrobacterium ) spp. , Azorhizobium caulinodans, Azorhizobium caulinodans , Azospirillum spp., Azotobacter spp ., Bradyrhizobium spp ., Burkholderia spp ., in particular Burkholderia cepacia (Previously known as Pseudomonas cepacia ), Gigaspora spp ., or Gigaspora monosporum , Glomus spp . , Laccaria spp ., Lactobacillus buchneri , Paraglomus spp., Pisolithus tinctorus , Pseudomonas spp., Rhizobium ) spp ., especially Rhizobium trifolii , Rhizopogon spp., Scleroderma spp., Suillus spp ., Streptomyces spp. .

Examples of products formed by microorganisms and plant extracts, including proteins and secondary metabolites, which can be applied or used as biological pesticides are:

Allium sativum, Artemisia absinthium, azadirachtin, BioKeeper WP, Cassia nigricans, Celastrus angulatus, Kenopodium antelmin Chenopodium anthelminticum, Chitin, Armor-Zen, Dryopteris filix-mas, Equisetum arvense, Fortune Aza, Pungastov ( Fungastop), Heads Up (Chenopodium quinoa saponin extract), Pyrethrum/Pyrethrins, Quassia amara, Quercus, Quillaja , Regalia, "Requiem™ Insecticide", Rotenone, Lyania/Lyanodine, Symphytum officinale, Tanacetum vulgare, Thymol, Triact 70, TriCon, Trophae Olive oil, including extracts of Tropaeulum majus, Urtica dioica, Veratrin, Viscum album, Brassicaceae, especially rapeseed powder or mustard powder Biopesticidal/acaricidal active substances obtained from, in particular unsaturated fats/carboxylic acids with C ₁₆ -C ₂₀ carbon chain length as active ingredient contained, for example, in products under the tradename FLiPPER®.

Emollient as a blending component

Compounds of formula (I) may be used as laxatives, such as for example benoxacor, cloquintocet (-mesyl), thiomethrinil, cyprosulfamide, dichlormid, fenchlorazole (-ethyl), fenchlorim , flurazole, fuluxofenim, furilazole, isoxadifen (-ethyl), mefenpyr (-diethyl), naphthalic anhydride, oxabetrinyl, 2-methoxy-N-({4-[ (methylcarbamoyl)amino]phenyl}sulfonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS 71526-07-3) , 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (CAS 52836-31-4).

plants and plant parts

All plants and plant parts can be treated according to the present invention. Plants herein include all plants and plant parts, such as desired and undesirable wild plants or crops (including naturally occurring crops), for example cereals (wheat, rice, triticale, barley, rye, oats), maize, soybeans, potatoes , beets, sorghum, tomatoes, peppers, cucumbers, melons, carrots, watermelons, onions, lettuce, spinach, leeks, beans, Brassica oleracea (eg cabbage) and other plant species, cotton , tobacco, fluids, and also fruit plants (fruits such as apples, pears, citrus fruits and grapes). Agricultural crops, including transgenic plants and including plant varieties that may or may not be protected by the rights of plant breeders, may be obtained through conventional breeding and optimization methods or by biotechnology and genetic engineering methods or combinations of these methods. It may be a plant that can be obtained through Plants are to be understood as meaning all stages of development, such as seeds, seedlings, young (immature) plants to mature plants. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoots, leaves, flowers and roots, examples provided being leaves, thorns, stalks, stems, flowers, fruit bodies, fruits and seeds , and also tubers, roots, and rhizomes. Plant parts also include harvested plants or harvested plant parts and asexual and generative propagation material such as seedlings, tubers, rhizomes, grafts and seeds.

The treatment according to the present invention of plants and plant parts with compounds of formula (I) is carried out via customary treatment methods, for example in the case of dipping, spraying, evaporation, misting, spreading, painting, pouring, and propagation materials, Especially in the case of seeds, this is also done directly or by applying one or more envelopes, allowing the compound to act on the surroundings, environment or storage space.

As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as hybridization or protoplast fusion, and also parts thereof are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained through genetic engineering methods (genetically modified organisms), and parts thereof, are treated, if appropriate in combination with conventional methods. The term "part" or "part of a plant" or "plant part" is as explained above. The present invention is particularly preferably used to treat plants of each commercially common plant cultivar or those in use. Plant cultivars are to be understood as meaning plants with new properties ("traits") and obtained through conventional breeding, mutagenesis, or recombinant DNA techniques. They can be cultivars, varieties, biotypes and genotypes.

Transgenic plants, seed treatment and integration events

According to the present invention, the compounds of formula (I) are used to treat transgenic plants, plant cultivars or plant parts that have received genetic material imparting advantageous and/or useful properties (traits) to those plants, plant cultivars or plant parts, respectively. It can be advantageously used for Therefore, it is contemplated that the present invention may be combined with one or more recombinant trait or transformation event(s) or combinations thereof. For the purposes of this application, a transformation event is produced through the insertion of a particular recombinant DNA molecule at a particular location (locus) within the chromosome of the plant genome. Insertion creates a new DNA sequence called an "event" and is characterized by the inserted recombinant DNA molecule and an amount of genomic DNA flanking/immediately adjacent to both ends of the inserted DNA. Such trait(s) or transformation event(s) include, but are not limited to, pest resistance, water use efficiency, yield performance, drought tolerance, seed quality, improved nutritional quality, hybrid seed production, and herbicide tolerance. , the trait is measured in comparison to plants lacking this trait or such transformation event. Specific examples of such advantageous and/or useful properties (traits) are better plant growth, vigor, stress tolerance, stability, shelter tolerance, nutrient uptake, plant nutrition and/or yield, especially improved growth, increased to high or low temperatures. increased tolerance, increased tolerance to drought or water or soil salt levels, increased flowering performance, easier harvesting, accelerated ripening, higher yield, higher quality and/or higher nutritional value of the harvested product, harvested better shelf life stability and/or processability of the product, and increased resistance or resistance to animal and microbial pests such as insects, arachnids, nematodes, mites and slugs and snails.

Amongst the DNA sequences encoding proteins conferring properties of resistance or resistance to such animal and microbial pests, particularly insects, the genetic material of Bacillus thuringiensis encoding the Bt protein, which has been extensively described in the literature and is sufficiently known to those skilled in the art. can be mentioned in particular. Proteins extracted from bacteria such as Photorhabdus are also referred to (WO97/17432 and WO98/08932). In particular, the CrylA, CryIAb, CryIAc, CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF proteins or toxic fragments thereof, and also hybrids or combinations thereof, in particular Cry1F proteins or hybrids derived from Cry1F proteins (e.g. hybrids Cry1A-Cry1F protein or a toxic fragment thereof), a protein of the Cry1A type or a toxic fragment thereof, preferably a Cry1Ac protein or a hybrid derived from a Cry1Ac protein (eg a hybrid Cry1Ab-Cry1Ac protein) or a Cry1Ab or Bt2 protein or a toxic fragment thereof , Cry2Ae, Cry2Af or Cry2Ag protein or toxic fragments thereof, Cry1A.105 protein or toxic fragments thereof, VIP3Aa19 protein, VIP3Aa20 protein, VIP3A protein, produced in COT202 or COT203 cotton events [Estruch et al. (1996), Proc Natl Acad Sci US A. 28;93(11):5389-94, VIP3Aa protein or toxic fragment thereof, Cry protein as described in WO2001/47952, Xenolabdus ( Xenorhabdus ) (described in WO98/50427), Serratia (particularly S. entomophila ( S. entomophila ) or Photorhabdus ) Insecticidal proteins from strains of the species, such as those described in WO98/08932 Particular mention will be made of the Bt-Cry or VIP proteins, including the Tc protein from Photolabdus as This also means that some amino acids (1-10, preferably 1-5) differ from any sequence named above, especially the sequence of a toxic fragment thereof, or are fused with transit peptides such as plastid transit peptides or other proteins or peptides. Also included are any variants or mutants of any one of the proteins.

Another particularly highlighting example of this property is the conferred resistance to one or more herbicides, such as imidazolinones, sulfonylureas, glyphosate or phosphinotricin. Of the DNA sequences encoding proteins that confer resistance to certain herbicides to transformed plant cells and plants, the streptomyces described in WO2009/152359 that confer resistance to bar or PAT genes or glufosinate herbicides Suitable EPSPS (5- enolpyruvylshikimate -3-phosphate synthase ), a gene encoding glyphosate-n-acetyltransferase or a gene encoding glyphosate oxidoreductase. Additional suitable herbicide tolerance traits include at least one ALS (acetolactate synthase) inhibitor (eg WO2007/024782), a mutated Arabidopsis ALS/AHAS gene (eg US Patent 6,855,533), 2 Gene encoding 2,4-D-monooxygenase, which confers resistance to ,4-D (2,4-dichlorophenoxyacetic acid), and dicamba (3,6-dichloro-2-methoxybenzoic acid ) contains a gene encoding dicamba monooxygenase that confers resistance to.

Further particularly emphatic examples of this property are, for example, systemic acquired resistance (SAR), increased resistance to phytopathogenic fungi, bacteria, and/or viruses due to cystemin, phytoalexins, elicitors, and also resistance genes and correspondingly expressed proteins and toxins.

Particularly useful transformation events in transgenic plants or plant cultivars that can be preferably treated according to the present invention include: Event 531/ PV-GHBK04 (cotton, insect control, described in WO2002/040677), Event 1143- 14A (cotton, insect control, not deposited, described in WO2006/128569); Case 1143-51B (cotton, insect control, not deposited, described in WO2006/128570); Event 1445 (cotton, herbicide tolerance, not deposited, described in US-A 2002-120964 or WO2002/034946); Event 17053 (rice, herbicide tolerance, deposited as PTA-9843, described in WO2010/117737); Event 17314 (rice, herbicide tolerance, deposited as PTA-9844, described in WO2010/117735); Case 281-24-236 (cotton, insect control—herbicide tolerance, deposited as PTA-6233, described in WO2005/103266 or US-A 2005-216969); Case 3006-210-23 (cotton, insect control—herbicide tolerance, deposited as PTA-6233, described in US-A 2007-143876 or WO2005/103266); Event 3272 (corn, quality trait, deposited as PTA-9972, described in WO2006/098952 or US-A 2006-230473); Case 33391 (wheat, herbicide tolerance, deposited as PTA-2347, described in WO2002/027004), case 40416 (corn, insect control—herbicide tolerance, deposited as ATCC PTA-11508, described in WO 11/075593); Case 43A47 (corn, insect control—herbicide tolerance, deposited as ATCC PTA-11509, described in WO2011/075595); Case 5307 (corn, insect control, deposited as ATCC PTA-9561, described in WO2010/077816); Event ASR-368 (bentgrass, herbicide tolerance, deposited as ATCC PTA-4816, described in US-A 2006-162007 or WO2004/053062); Event B16 (corn, herbicide tolerance, not deposited, described in US-A 2003-126634); Event BPS-CV127-9 (soybean, herbicide tolerance, deposited as NCIMB no. 41603, described in WO2010/080829); Case BLRl (rape, recovery of male sterility, deposited as NCIMB No. 41193, described in WO2005/074671), case CE43-67B (cotton, insect control, deposited as DSM ACC2724, deposited as US-A 2009-217423 or WO2006/128573 write); Case CE44-69D (cotton, insect control, not deposited, described in US-A 2010-0024077); Case CE44-69D (cotton, insect control, not deposited, described in WO2006/128571); Case CE46-02A (cotton, insect control, not deposited, described in WO2006/128572); Incident COT102 (cotton, insect control, not deposited, described in US-A 2006-130175 or WO2004/039986); Case COT202 (cotton, insect control, not deposited, described in US-A 2007-067868 or WO2005/054479); Incident COT203 (cotton, insect control, not deposited, described in WO2005/054480); Case DAS21606-3/1606 (soybean, herbicide tolerance, deposited as PTA-11028, described in WO2012/033794), case DAS40278 (maize, herbicide tolerance, deposited as ATCC PTA-10244, described in WO2011/022469); Incident DAS-44406-6/pDAB8264.44.06.l (soybean, herbicide tolerance, deposited as PTA-11336, described in WO2012/075426), incident DAS-14536-7 /pDAB8291.45.36.2 (soybean, herbicide tolerance, PTA deposited as -11335, described in WO2012/075429), incident DAS-59122-7 (corn, insect control—herbicide tolerance, deposited as ATCC PTA 11384, described in US-A 2006-070139); Incident DAS-59132 (corn, insect control—herbicide tolerance, not deposited, described in WO2009/100188); Event DAS68416 (soybean, herbicide tolerance, deposited as ATCC PTA-10442, described in WO2011/066384 or WO2011/066360); Event DP-098140-6 (corn, herbicide tolerance, deposited as ATCC PTA-8296, described in US-A 2009-137395 or WO 08/112019); Event DP-305423-1 (soybean, quality trait, not deposited, described in US-A 2008-312082 or WO2008/054747); Event DP-32138-1 (corn, hybridization system, deposited as ATCC PTA-9158, described in US-A 2009-0210970 or WO2009/103049); Event DP-356043-5 (soybean, herbicide tolerance, deposited as ATCC PTA-8287, described in US-A 2010-0184079 or WO2008/002872); Incident EE-I (eggplant, insect control, not deposited, described in WO 07/091277); Event Fil 17 (corn, herbicide tolerance, deposited as ATCC 209031, described in US-A 2006-059581 or WO 98/044140); Case FG72 (soybean, herbicide tolerance, deposited as PTA-11041, described in WO2011/063413), case GA21 (maize, herbicide tolerance, deposited as ATCC 209033, described in US-A 2005-086719 or WO 98/044140); Event GG25 (corn, herbicide tolerance, deposited as ATCC 209032, described in US-A 2005-188434 or WO98/044140); Incident GHB119 (cotton, insect control—herbicide tolerance, deposited as ATCC PTA-8398, described in WO2008/151780); Incident GHB614 (cotton, herbicide tolerance, deposited as ATCC PTA-6878, described in US-A 2010-050282 or WO2007/017186); Case GJ11 (corn, herbicide tolerance, deposited as ATCC 209030, described in US-A 2005-188434 or WO98/044140); Event GM RZ13 (sugar beet, viral resistance, deposited as NCIMB-41601, described in WO2010/076212); Event H7-1 (sugar beet, herbicide tolerance, deposited as NCIMB 41158 or NCIMB 41159, described in US-A 2004-172669 or WO 2004/074492); Event JOPLIN1 (wheat, disease resistance, not deposited, described in US-A 2008-064032); Event LL27 (soybean, herbicide tolerance, deposited as NCIMB41658, described in WO2006/108674 or US-A 2008-320616); Event LL55 (soybean, herbicide tolerance, deposited as NCIMB 41660, described in WO 2006/108675 or US-A 2008-196127); Case LL cotton25 (cotton, herbicide tolerance, deposited as ATCC PTA-3343, described in WO2003/013224 or US-A 2003-097687); Incident LLRICE06 (rice, herbicide tolerance, deposited as ATCC 203353, described in US 6,468,747 or WO2000/026345); case LLRice62 (rice, herbicide tolerance, deposited as ATCC 203352, described in WO2000/026345), case LLRICE601 (rice, herbicide tolerance, deposited as ATCC PTA-2600, described in US-A 2008-2289060 or WO2000/026356); Event LY038 (corn, quality trait, deposited as ATCC PTA-5623, described in US-A 2007-028322 or WO2005/061720); Incident MIR162 (corn, insect control, deposited as PTA-8166, described in US-A 2009-300784 or WO2007/142840); Event MIR604 (corn, insect control, not deposited, described in US-A 2008-167456 or WO2005/103301); Case MON15985 (cotton, insect control, deposited as ATCC PTA-2516, described in US-A 2004-250317 or WO2002/100163); Incident MON810 (corn, insect control, not deposited, described in US-A 2002-102582); Case MON863 (corn, insect control, deposited as ATCC PTA-2605, described in WO2004/011601 or US-A 2006-095986); Incident MON87427 (corn, pollination control, deposited as ATCC PTA-7899, described in WO2011/062904); Event MON87460 (corn, stress tolerance, deposited as ATCC PTA-8910, described in WO2009/111263 or US-A 2011-0138504); Case MON87701 (soybean, insect control, deposited as ATCC PTA-8194, described in US-A 2009-130071 or WO2009/064652); Event MON87705 (soybean, quality trait—herbicide tolerance, deposited as ATCC PTA-9241, described in US-A 2010-0080887 or WO2010/037016); Case MON87708 (soybean, herbicide tolerance, deposited as ATCC PTA-9670, described in WO2011/034704); case MON87712 (soybean, yield, deposited as PTA-10296, described in WO2012/051199), case MON87754 (soybean, quality trait, deposited as ATCC PTA-9385, described in WO2010/024976); Event MON87769 (soybean, quality trait, deposited as ATCC PTA-8911, described in US-A 2011-0067141 or WO2009/102873); Case MON88017 (corn, insect control—herbicide tolerance, deposited as ATCC PTA-5582, described in US-A 2008-028482 or WO2005/059103); Case MON88913 (cotton, herbicide tolerance, deposited as ATCC PTA-4854, described in WO2004/072235 or US-A 2006-059590); Case MON88302 (rapeseed, herbicide tolerance, deposited as PTA-10955, described in WO2011/153186), case MON88701 (cotton, herbicide tolerance, deposited as PTA-11754, described in WO2012/134808), case MON89034 (corn, insect control, deposited as ATCC PTA-7455, described in WO 07/140256 or US-A 2008-260932); Case MON89788 (soybean, herbicide tolerance, deposited as ATCC PTA-6708, described in US-A 2006-282915 or WO2006/130436); Incident MSl 1 (rapeseed, pollination control - herbicide tolerance, deposited as ATCC PTA-850 or PTA-2485, described in WO2001/031042); Event MS8 (rapeseed, pollination control—herbicide tolerance, deposited as ATCC PTA-730, described in WO2001/041558 or US-A 2003-188347); Event NK603 (corn, herbicide tolerant, deposited as ATCC PTA-2478, described in US-A 2007-292854); Event PE-7 (rice, insect control, not deposited, described in WO2008/114282); Incident RF3 (rapeseed, pollination control—herbicide tolerance, deposited as ATCC PTA-730, described in WO2001/041558 or US-A 2003-188347); Event RT73 (rapeseed, herbicide tolerance, not deposited, described in WO2002/036831 or US-A 2008-070260); Case SYHT0H2 / SYN-000H2-5 (soybean, herbicide tolerance, deposited as PTA-11226, described in WO2012/082548), case T227-1 (sugar beet, herbicide tolerance, not deposited, WO2002/44407 or US-A 2009-265817 described in); Event T25 (corn, herbicide tolerance, not deposited, described in US-A 2001-029014 or WO2001/051654); Case T304-40 (cotton, insect control—herbicide tolerance, deposited as ATCC PTA-8171, described in US-A 2010-077501 or WO2008/122406); Case T342-142 (cotton, insect control, not deposited, described in WO2006/128568); Case TC1507 (corn, insect control—herbicide tolerance, not deposited, described in US-A 2005-039226 or WO2004/099447); Case VIP1034 (corn, insect control—herbicide tolerance, deposited as ATCC PTA-3925, described in WO2003/052073), case 32316 (corn, insect control—herbicide tolerance, deposited as PTA-11507, described in WO2011/084632), case 4114 (corn, insect control—herbicide tolerance, deposited as PTA-11506, described in WO2011/084621), case EE-GM1/LL27 or case EE-GM2/LL55 (WO2011/063413A2) arbitrarily stacked case EE-GM3 / FG72 (soybean, herbicide tolerant, ATCC registration number PTA-11041), incident DAS-68416-4 (soybean, herbicide tolerant, ATCC registration number PTA-10442, WO2011/066360Al), incident DAS-68416-4 (soybean, herbicide tolerant) , ATCC registration number PTA-10442, WO2011/066384Al), case DP-040416-8 (corn, insect control, ATCC registration number PTA-11508, WO2011/075593Al), case DP-043A47-3 (corn, insect control, ATCC Registration No. PTA-11509, WO2011/075595Al), Case DP-004114-3 (Maize, Insect Control, ATCC Registration No. PTA-11506, WO2011/084621Al), Case DP-032316-8 (Maize, Insect Control, ATCC Registration No. PTA-11507, WO2011/084632Al), incident MON-88302-9 (rapeseed, herbicide tolerance, ATCC registration number PTA-10955, WO2011/153186Al), incident DAS-21606-3 (soybean, herbicide tolerance, ATCC registration number PTA- 11028, WO2012/033794A2), incident MON-87712-4 (soybean, quality trait, ATCC registration number PTA-10296, WO2012/051199A2), incident DAS-44406-6 (soybean, layered herbicide tolerance, ATCC registration number PTA- 11336, WO2012/075426Al), Incident DAS-14536-7 (soybean, layered herbicide tolerance, ATCC registration number PTA-11335, WO2012/075429Al), incident SYN-000H2-5 (soybean, herbicide tolerance, ATCC registration number PTA-11226, WO2012/082548A2), Case DP-061061-7 (rapeseed, herbicide tolerance, accession number not available, WO2012071039Al), case DP-073496-4 (rapeseed, herbicide tolerance, accession number not available, US2012131692), case 8264.44.06.1 (soybean, layered herbicide Tolerance, registration number PTA-11336, WO2012075426A2), event 8291.45.36.2 (soybean, layered herbicide tolerance, registration number PTA-11335, WO2012075429A2), event SYHT0H2 (soybean, ATCC registration number PTA-11226, WO2012/082548A2), event MON88701 (cotton, ATCC registration number PTA-11754, WO2012/134808Al), incident KK179-2 (alfalfa, ATCC registration number PTA-11833, WO2013/003558Al), incident pDAB8264.42.32.1 (soybean, layered herbicide tolerance, ATCC registration number PTA-11993, WO2013/010094Al), case MZDT09Y (corn, ATCC registration number PTA-13025, WO2013/012775Al).

Further, this list of such transformation event(s) is provided by the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA), www.aphis You can find them on their website at .usda.gov. In the case of this application, the status of this list at the filing date of this application is relevant.

In a transgenic plant, the genes/events conferring the desired trait in question may also be present in combination with each other in the transgenic plant. Examples of transgenic plants that may be mentioned are important crops, such as cereals (wheat, rice, triticale, barley, rye, oats), maize, soybeans, beans, potatoes, sugar beets, sugar cane, tomatoes, peas, and other types plants, including cotton, tobacco, rapeseed, and also fruit plants (fruits being apples, pears, citrus fruits and grapes), with particular emphasis on corn, soybean, wheat, rice, potato, cotton, sugar cane, tobacco and rapeseed do. Traits that are particularly emphasized are increased tolerance of plants to one or more herbicides, including increased tolerance of plants to insects, arachnids, nematodes, and slugs and snails.

Commercially available examples of such plants, plant parts or plant seeds which can be preferably treated according to the present invention are commercial products such as GENUITY®, DROUGHTGARD®, SMARTSTAX®, RIB COMPLETE®, ROUNDUP READY®, VT DOUBLE PRO®, Includes plant seeds sold or distributed under the trade names VT TRIPLE PRO®, BOLLGARD II®, ROUNDUP READY 2 YIELD®, YIELDGARD®, ROUNDUP READY® 2 XTEN ^DTM , INTACTA RR2 PRO®, VISTIVE GOLD® and/or XTENDFLEX® .

Crop protection - type of treatment

The treatment of plants and plant parts with the compounds of formula (I) can be carried out using conventional treatment methods, for example by dipping, spraying, atomizing, irrigation, evaporation, dusting, misting, scattering, foaming, painting, spreading, pouring, By irrigation (drench), by drip irrigation, around grazes, on habitats or storage spaces or directly, in the case of propagation material, in particular in the case of seeds, as a powder for dry seed treatment, as a solution for liquid seed treatment , as a water-soluble powder for slurry treatment, by enclosing, by coating with one or more outer skins, etc. Furthermore, it is possible to apply the compound of formula (I) by an ultra-low dose method or it is possible to inject the compound of formula (I) per se or its application form into the soil.

A preferred direct treatment of plants is foliar application, ie the application of the compound of formula (I) to the leaves, in which case the frequency and rate of application should be adjusted according to the level of infestation of the pest in question.

In the case of systemically active active compounds, the compounds of formula (I) also gain access to the plant through the root system. The plant is then treated through the application of a compound of formula (I) onto the plant's habitat. This can be done, for example, through drenching, or by admixture to soil or nutrient solutions, i.e. impregnation of the plant locus (eg soil or hydroponic system) with the liquid form of the compound of formula (I), or soil By application, ie the introduction of a compound of formula (I) according to the invention in solid form (eg in the form of granules) into the locus of the plant, or by drip application (frequently also referred to as "chemical irrigation") , ie by liquid application of a compound of formula (I) according to the invention at a defined location adjacent to the plant with varying amounts of water for a period of time via a surface or underground drip line. In the case of rice crops, this can also be done by metering in the compound of formula (I) in solid application form (eg as granules) into the flooded paddy field.

digital technology

The compounds of the present invention can be used in combination with models embedded in computer programs, for example for site-specific crop management, satellite farming, precision farming or precision agriculture. These models are intended to optimize profitability, sustainability and environmental protection from a variety of sources such as soil, weather, crops (eg, type, growing season, plant health), weeds (eg, growing season), disease, pests. , data from nutrients, water, water biomass, satellite data, and yield are used to support site-specific management of agricultural sites. In particular, these models can help optimize agronomic decisions, control the accuracy of pesticide application, and record operations performed.

By way of example, a compound of the present invention may be applied to a crop according to an appropriate dosage regimen where the model simulates the occurrence of a pest and calculates that a threshold has been reached for recommending application of a compound of the present invention to the crop.

Commercially available systems containing agricultural models are, for example, Climate Corporation's FieldScripts™, BASF's Xarvio™, John Deere's AGLogic™, and the like.

The compounds of the present invention may also be used in combination with smart spraying equipment such as, for example, farm vehicles such as tractors, robots, helicopters, airplanes, unmanned aerial vehicles (UAVs) such as drones, or attached to or housed in drip spraying or precision spraying equipment. there is. Such equipment is generally configured to analyze input sensors (such as, for example, cameras) and input data, and to apply a compound of the present invention to a crop (the respective weed) in a specific and precise manner based on the analysis of the input data. and a processing unit configured to provide a decision. The use of such smart spraying equipment generally also includes a positioning system (eg, a GPS receiver) to localize the recorded data and steer or control the farm vehicle; It requires a geographic information system (GIS) that displays information on understandable maps, and suitable farm vehicles to perform essential farm tasks such as spraying.

In one example, pests can be detected from photos taken with a camera. In one example, pests may be identified and/or classified based on such photographs. This identification and/or classification may utilize image processing algorithms. Such image processing algorithms may use machine learning algorithms, such as trained neutral networks, decision trees, and may use artificial intelligence algorithms. In this way, the compounds described herein can be applied only when needed.

seed treatment

The control of pests by treatment of plant seeds has been known for a long time and is the subject of continuous improvement. However, the treatment of seeds entails a series of problems that cannot always be solved in a satisfactory manner. It is therefore desirable to develop methods for protecting seeds and germinating plants which eliminate, or at least significantly reduce, the further application of agrochemicals during storage of the plants, after sowing or after emergence of the plants. It is further desirable to optimize the amount of active compound applied in such a way to provide optimum protection to the seed and germinating plants from attack by pests, without damage to the plant per se by the active compound applied. In particular, methods for seed treatment must also take into account the inherent insecticidal or nematicidal properties of pest-resistant or pest-resistant transgenic plants in order to obtain optimum protection of the seed and also of the germinating plant at a minimum cost for the pesticides applied. .

Therefore, the present invention in particular also relates to a method for protecting seed and germinating plants from attack by pests by treating the seed with one of the compounds of formula (I). The method according to the present invention for protecting seeds and germinating plants against attack by pests further comprises a method of treating the seed with a compound of formula (I) and a mixed component simultaneously or sequentially in one operation. It further includes a method of treating the seed with the compound of formula (I) and the mixing component at different times.

Similarly the present invention relates to the use of compounds of formula (I) for the treatment of seed to protect the seed and the final plant from pests.

Furthermore, the present invention relates to seed treated with a compound of formula (I) according to the present invention to provide protection from pests. The present invention also relates to seed treated simultaneously with a compound of formula (I) and a mixing component. The present invention also relates to seed treated at different times with the compound of formula (I) and the mixing component. In the case of seed treated at different times with the compound of formula (I) and the mixing component, the individual substances may be present on the seed in different layers. Here, the layer comprising the compound of formula (I) and the mixing component may optionally be spaced apart via an intermediate layer. The present invention also relates to seeds wherein the compound of formula (I) and the mixing component are applied as a component of the hull or as an additional layer or as additional layers added to the hull.

Furthermore, the present invention relates to seeds in which, after treatment with a compound of formula (I), a film-coating process is performed to prevent dust abrasion on the seeds.

One of the advantages encountered with the systematic action of the compounds of formula (I) is that by treating the seeds, not only the seeds themselves but also the plants produced therefrom are protected from pests after emergence. In this way, immediate treatment of the crop at the time of sowing or immediately thereafter can be omitted.

A further advantage should be considered that by treatment of the seed with a compound of formula (I), germination and emergence of the treated seed can be enhanced.

Similarly, it should be considered as a further advantage that the compounds of formula (I) can in particular also be used in transgenic seeds.

Furthermore, the compounds of formula (I) can be applied in combination with compositions or compounds of signaling technology, so as to form symbionts such as, for example, rhizobia, mycorrhizae and/or intestinal bacteria or results in better colonization by fungi, and/or optimized nitrogen fixation.

The compounds of formula (I) are suitable for the protection of seeds of any plant variety used in agriculture, greenhouses, forestry or horticulture. In particular, it includes cereals (e.g. wheat, barley, rye, millet and oats), maize, cotton, soybeans, rice, potatoes, sunflowers, coffee, tobacco, canola, rapeseed, beets (e.g. sugar beets and fodder beets). , seeds of peanuts, vegetables (eg tomatoes, cucumbers, beans, rapeseeds, onions and lettuce), fruit plants, lawns, and ornamental plants. Of particular importance is the treatment of seeds of cereals (eg wheat, barley, rye and oats), maize, soybean, cotton, canola, rapeseed, vegetables and rice.

As already mentioned above, the treatment of transgenic seed with compounds of formula (I) is also of particular interest. It usually takes the form of a seed of a plant comprising at least one heterologous gene directing the expression of a polypeptide having in particular insecticidal and/or nematicidal properties. The heterologous gene in the transgenic seed may be a microorganism such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Glio It may originate from Gliocladium. The present invention is particularly suitable for the treatment of transgenic seed comprising at least one heterologous gene originating from a Bacillus species. A heterologous gene derived from Bacillus thuringiensis is particularly preferred.

In the context of the present invention, the compounds of formula (I) are applied to seed. Preferably, the seed is treated sufficiently stable to avoid damage during treatment. In general, seeds may be treated at any point between harvest and sowing. The commonly used seed has been separated from the plant and has no cobs, husks, stems, hulls, hairs or fruit flesh. For example, it is also possible to use seeds that have been harvested, cleaned and dried to a moisture content acceptable for storage. Alternatively, it is also possible to use seeds that have been dried, eg treated with water and then dried again, eg primed. In the case of rice seeds, it is also possible to use seeds impregnated with water, for example, to a certain stage of rice germination ("pigeon breast stage"), which stimulates germination and more uniform emergence.

When treating seed, care is generally taken to ensure that the amount of the compound of formula (I) and/or the amount of further additives applied to the seed is chosen so that the germination of the seed is not adversely affected or the resulting plant is not damaged. ah do This must be ensured in particular in the case of active compounds which may exhibit phytotoxic effects at certain application rates.

Generally, the compound of formula (I) is applied to the seed in the form of a suitable formulation. Suitable formulations and seed treatment methods are known to those skilled in the art.

The compounds of formula (I) can be converted into customary seed-dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seeds, and also ULV formulations.

These preparations combine the compounds of formula (I) with customary additives, such as, for example, conventional extenders and also solvents or diluents, colorants, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, tackifiers, gibberellins, and also water and is prepared in a conventional manner.

The colorants which may be present in the seed-dressing formulations usable according to the invention are all colorants customary for this purpose. It is possible to use pigments sparingly soluble in water, or dyes soluble in water. Examples include Rhodamine B, C.I. Pigment Red 112 and C.I. It includes a dye known under the name Solvent Red 1.

Useful wetting agents which may be present in the seed-dressing formulations usable according to the invention are all substances which promote wetting and which are conventionally used in the formulation of chemical fertilizer active compounds. Preference is given to using alkylnaphthalenesulfonates, such as diisopropyl- or diisobutyl naphthalenesulfonate.

Useful dispersants and/or emulsifiers which may be present in the seed-dressing formulations usable according to the invention are all nonionic, anionic and cationic dispersants customary in the formulation of active chemical fertilizer ingredients. It may be desirable to use nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Suitable nonionic dispersants include, inter alia, ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers, and phosphated or sulfated derivatives thereof. Suitable anionic dispersants are in particular lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.

Antifoams which may be present in the seed-dressing formulations usable according to the invention are all foam-inhibiting substances customary in the formulation of active chemical fertilizer ingredients. Preference is given to using silicone defoamers and magnesium stearate.

Preservatives that may be present in the seed-dressing formulations according to the invention are all substances usable for this purpose in chemical fertilizer compositions. Examples include dichlorophen and benzyl alcohol hemiformal.

Secondary thickeners which may be present in the seed-dressing formulations usable according to the invention are all substances which can be used for this purpose in chemical fertilizer compositions. Cellulose derivatives, acrylic acid derivatives, xanthan, modified clay and finely divided silica are preferred.

Useful tackifiers which may be present in seed-dressing formulations usable according to the invention are all customary binders usable in seed-dressing products. Polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose may preferably be mentioned.

Gibberellins which may be present in the seed-dressing formulations usable according to the present invention are preferably gibberellins A1, A3 (= gibberellic acid), A4 and A7, with gibberellic acid being particularly preferably used. Gibberellins are known (see R. Wegler "Chemie der Pflanzenschutz- and Schadlingsbekampfungsmittel", vol. 2, Springer Verlag, 1970, pp. 401-412).

The seed-dressing formulations usable according to the invention can be used directly or after prior dilution with water to treat a wide variety of different types of seed. For example, concentrates or preparations obtainable therefrom by dilution with water are seeds of cereal grains such as wheat, barley, rye, oats and triticale, and also maize, rice, rapeseed, peas, soybeans, cotton, sunflower, soybean and beet. seeds, or other widely different plant seeds. The seed-dressing formulations usable according to the invention, or diluted use forms thereof, can also be used for dressing the seeds of transgenic plants.

In the case of treatment of seeds with seed-dressing formulations usable according to the invention, or use forms prepared therefrom with the addition of water, all mixing units customarily usable for seed dressing are useful. In particular, the procedure in seed dressing involves placing the seeds in a mixer, operating in batch or continuous operation, adding a particularly desired amount of seed-dressing formulation, either as such or after prior dilution with water, when the formulation is homogeneously distributed on the seeds. to mix everything. If appropriate, this is followed by a drying operation.

The application rates of the seed dressing formulations usable according to the invention can vary within relatively wide ranges. Guided by the specific content and seed of the compound of formula (I) in the preparation. The application rate of the compound of formula (I) is generally from 0.001 to 50 g per kilogram of seed, preferably from 0.01 to 15 g per kilogram of seed.

animal health

In the field of animal health, ie in the field of veterinary medicine, the compounds of formula (I) are active against animal parasites, in particular against ectoparasites or endoparasites. The term "internal parasites" includes in particular helminths and protozoa, such as coccidia. Ectoparasites are typically, preferably arthropods, especially insects or mites.

In the field of veterinary medicine, the compound of formula (I) with desirable endothermic toxicity is advantageous in warm-blooded animals, for controlling parasites occurring in animal breeding and livestock husbandry, breeding animals, zoo animals, laboratory animals, laboratory animals, and livestock. suitable for They are active against all or specific developmental stages of parasites.

Agricultural livestock include, for example, mammals such as sheep, goats, horses, donkeys, camels, buffaloes, rabbits, caribou, fallow deer and especially cattle and pigs; or poultry such as turkeys, ducks, geese, and especially chickens; or including fish and shellfish, for example in aquaculture; or, in some cases, an insect, such as a bee.

Domestic animals include, for example, mammals such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets, and especially dogs, cats, caged birds; Includes reptiles, amphibians or aquarium fish.

According to certain embodiments, the compound of formula (I) is administered to a mammal.

According to another particular embodiment, the compound of formula (I) is administered to birds, ie caged birds or in particular poultry.

The use of compounds of formula (I) for the control of animal parasites reduces disease, mortality and performance (meat, milk, wool, leather, egg honey, etc.) is intended to reduce or prevent

In the context of the field of animal health, the terms "control" or "controlling" as used herein mean that the compound of formula (I) is effective in reducing the incidence of the respective parasite to harmless levels in animals infected with such parasites. do. More particularly, as used herein, "controlling" means that the compound of Formula (I) is effective in killing, inhibiting the growth or inhibiting the multiplication of the respective parasite.

Exemplary arthropods include, without limitation:

From the order Anoplurida, for example Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenophotes (Solenopotes) spp.;

From the order Mallophagida and the suborders Amblycerina and Ischnocerina, for example Bovicola spp., Damalina spp., Felicola spp. ; Lepikentron spp., Menopon spp., Trichodectes spp., Trimenopon spp., Trinoton spp., Werneckiella spp ;

Diptera order and Nematocerina and Brachycerina suborders, for example Aedes spp., Anopheles spp., Atylotus spp., Braula ( Braula spp., Calliphora spp., Chrysomyia spp., Chrysops spp., Culex spp., Culicoides spp., Eusimulium spp., Fannia spp., Gasterophilus spp., Glossina spp., Haematobia spp., Haematopota spp., Hippobosca spp., Hybomitra spp., Hydrotaea spp., Hypoderma spp., Lipoptena spp., Lucilia spp. , Lutzomyia spp., Melophagus spp., Morellia spp., Musca spp., Odagmia spp., Oestrus spp. , Philipomyia spp., Phlebotomus spp., Rhinoestrus spp., Sarcophaga spp., Simulium spp., Stomoxys ) spp., Tabanus spp., Tipula spp., Wilhelmia spp., Wohlfahrtia spp.;

From the order Siphonapterida, for example Ceratophyllus spp.; Ctenocephalides spp., Pulex spp., Tunga spp., Xenopsis (Xenopsylla) spp.;

from the order Heteropterida, for example Cimex spp., Panstrongylus spp., Rhodnius spp., Triatoma spp.; as well as pests and sanitary pests from the order Blattarida.

Among the arthropods, mention may also be made, by way of example and without any limitation, of the following ticks (Acari):

From the subclass Acari (Acarina) and from the order Metastigmata, for example of the family Argasidae such as Argas spp., Ornithodorus spp., Otto Otobius spp., from the family Ixodidae, such as Amblyomma spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Ixodes spp., Rhipicephalus (Boophilus) spp., Rhipicephalus spp. (original genus of multi-host tick); From the order Mesostigmata such as Dermanyssus spp., Ornithonyssus spp., Pneumonyssus spp., Raillietia spp., Sternostoma ( Sternostoma) spp., Tropilaelaps spp., Varroa spp.; From the order Actinedida (Prostigmata), for example Acarapis spp., Cheyletiella spp., Demodex spp., Listrophorus ) spp., Myobia spp., Neotrombicula spp., Ornithocheyletia spp., Psorergates spp., Trombicula spp .; and from the order Acaridida (Astigmata), for example Acarus spp., Caloglyphus spp., Chorioptes spp., Cytodites ( Cytodites0 spp., Hypodectes spp., Knemidocoptes spp., Laminosioptes spp., Notoedres spp., Otodectes spp. , Psoroptes spp., Pterolichus spp., Sarcoptes spp., Trixacarus spp., Tyrophagus spp.

Exemplary parasitic protozoa include, without any limitation:

Mastigophora (Flagellata), such as:

Metamonada: from the order Diplomonadida, for example Giardia spp., Spironucleus spp.

Parabasala: from the order Trichomonadida, for example Histomonas spp., Pentatrichomonas spp., Tetratrichomonas spp., Trichomonas spp. , Tritrichomonas spp.

Euglenozoa: from the order Trypanosomatida, for example Leishmania spp., Trypanosoma spp.

Sarcomastigophora (Rhizopoda) such as Entamoebidae, eg Entamoeba spp., Centramoebidae, eg Acansameba ( Acanthamoeba) sp., Euamoebidae, such as Hartmanella sp.

Alveolata such as Apicomplexa (Sporozoa): eg Cryptosporidium spp.; From the order Eimeriida, for example Besnoitia spp., Cystoisospora spp., Eimeria spp., Hammondia spp., Isospora (Isospora) spp., Neospora spp., Sarcocystis spp., Toxoplasma spp.; from the order Adeleida, for example Hepatozoon spp., Klossiella spp.; from the order Haemosporida, for example Leucocytozoon spp., Plasmodium spp.; from the order Piroplasmida, for example Babesia spp., Ciliophora spp., Echinozoon spp., Theileria spp.; From the order Vesibuliferida, for example Balantidium spp., Buxtonella spp.

Microspora such as Encephalitozoon spp., Enterocytozoon spp., Globidium spp., Nosema spp., and also, for example, Myxozoa (Myxozoa) spp.

Worms pathogenic to humans or animals include, for example, acanthocephala, nematodes, pentastoma and platyhelminths (e.g. monogenea, cestodes) and trematodes).

Exemplary worms include, without any limitation:

Monogenea: For example: Dactylogyrus spp., Gyrodactylus spp., Microbothrium spp., Polystoma spp., Troglosse Troglocephalus spp.;

Cestodes: from the order Pseudophyllidea, for example: Bothridium spp., Diphyllobothrium spp., Diplogonoporus spp., Ichthiobot Ichthyobothrium spp., Ligula spp., Schistocephalus spp., Spirometra spp.

From the order Cyclophyllida, for example: Andyra spp., Anoplocephala spp., Avitellina spp., Bertiella spp., Cyto Cittotaenia spp., Davainea spp., Diorchis spp., Diplopylidium spp., Dipylidium spp., Echinococcus ) spp., Echinocotyle spp., Echinolepis spp., Hydatigera spp., Hymenolepis spp., Joyeuxiella spp., Meso Mesocestoides spp., Moniezia spp., Paranoplocephala spp., Raillietina spp., Stilesia spp., Taenia ( Taenia) spp., Thysaniezia spp., Thysanosoma spp.

Trematodes: from the class Digenea, for example: Austrobilharzia spp., Brachylaima spp., Calicophoron spp., Catatropis (Catatropis) spp., Clonorchis spp. Collyriclum spp., Cotylophoron spp., Cycocoelum spp., Dicrocoelium spp., Diplostomum spp., Echinocasmus (Echinochasmus) spp., Echinoparyphium spp., Echinostoma spp., Eurytrema spp., Fasciola spp., Fasciolides spp., Fasciolopsis spp., Fischoederius spp., Gastrothylacus spp., Gigantobilharzia spp., Gigantocotyle spp., Heterophyses (Heterophyes) spp., Hypoderaeum spp., Leucochloridium spp., Metagonimus spp., Metorchis spp., Nanophyetus ) spp., Notocotylus spp., Opisthorchis spp., Ornithobilharzia spp., Paragonimus spp., Paramphistomum spp. , Plagiorchis spp., Posthodiplostomum spp., Prosthogonimus spp., Schistosoma spp., Trichobilharzia spp. , Troglotrema spp., Typhlocoelum spp.

Nematodes: from the order Trichinellida, for example: Capillaria spp., Eucoleus spp., Paracapillaria spp., Trichinella ) spp., Trichomosoides spp., Trichuris spp.

From the order Tylenchida, for example: Micronema spp., Parastrongyloides spp., Strongyloides spp.

From the order Rhabditina, for example: Aelurostrongylus spp., Amidostomum spp., Ancylostoma spp., Angiostrongylus ) spp., Bronchonema spp., Bunostomum spp., Chabertia spp., Cooperia spp., Cooperioides spp., Crenoso Crenosoma spp., Cyathostomum spp., Cyclococercus spp., Cyclodontostomum spp., Cylicocyclus spp., Cylicostephanus spp., Cylindropharynx spp., Cystocaulus spp., Dictyocaulus spp., Elaphostrongylus spp., Filaroides spp ., Globocephalus spp., Graphidium spp., Gyalocephalus spp., Haemonchus spp., Heligmosomoides spp., Hios Hyostrongylus spp., Marshallagia spp., Metastrongylus spp., Muellerius spp., Necator spp., Nematodylus ( Nematodirus) spp., Neostrongylus spp., Nippostrongylus spp., Obeliscoides (Obelisco) ides) spp., Oesophagodontus spp., Oesophagostomum spp., Olulanus spp.; Ornithostrongylus spp., Oslerus spp., Ostertagia spp., Paracooperia spp., Paracrenosoma spp., Para Parafilaroides spp., Parelaphostrongylus spp., Pneumocaulus spp., Pneumostrongylus spp., Poteriostomum spp., Protostrongylus spp., Spicocaulus spp., Stephanurus spp., Strongylus spp., Syngamus spp., Telador Teladorsagia spp., Trichonema spp., Trichostrongylus spp., Triodontophorus spp., Troglostrongylus spp., Uncina Ria (Uncinaria) spp.

from the order Spirurida, for example: Acanthocheilonema spp., Anisakis spp., Ascaridia spp.; Ascaris spp., Ascarops spp., Aspiculuris spp., Baylisascaris spp., Brugia spp., Sercopithiphilaria (Cercopithifilaria) spp., Crassicauda spp., Dipetalonema spp., Dirofilaria spp., Dracunculus spp.; Traschia spp., Enterobius spp., Filaria spp., Gnathostoma spp., Gongylonema spp., Habronema spp ., Heterakis spp.; Litomosoides spp., Loa (Loa0 spp., Onchocerca spp., Oxyuris spp., Parabronema spp., Parafilaria spp ., Parascaris spp., Passalurus spp., Physaloptera spp., Probstmayria spp., Pseudofilaria spp., Setaria (Setaria) spp., Skjrabinema spp., Spirocerca spp., Stephanofilaria spp., Strongyluris spp., Syphacia spp ., Thelazia spp., Toxascaris spp., Toxocara spp., Wuchereria spp.

Acantocephala: from the order Oligacanthorhynchida, for example: Macracanthorhynchus spp., Prosthenorchis spp.; From the order Moniliformida: eg Moniliformis spp.,

from the order Polymorphida, for example: Filicollis spp.; From the order Echinorhynchida, for example Acanthocephalus spp., Echinorhynchus spp., Leptorhynchoides spp.

Pentastoma: from the order Porocephalida, eg Linguatula spp.

In the field of veterinary medicine and animal husbandry, the administration of the compounds of formula (I) is carried out by methods generally known in the art, such as enteral, parenteral, dermal or nasal, in the form of suitable preparations. Administration can be prophylactic, mass prophylactic or therapeutic.

Thus, one embodiment of the present invention refers to a compound of formula (I) for use as a drug.

Another aspect relates to a compound of formula (I) for use as an anti-endoparasitic agent.

Another particular embodiment refers to compounds of formula (I) for use as antihelminthicides, more particularly for use as nematocides, miticides, acaricides or acaricides.

Another particular aspect relates to a compound of formula (I) for use as an antiprotozoal agent.

Another aspect relates to compounds of formula (I) for use as antiectoparasitic agents, in particular arthropod agents, more particularly as insecticides or acaricides.

A further aspect of the present invention is a veterinary preparation comprising an effective amount of at least one compound of formula (I) and at least one of: a pharmaceutically acceptable excipient (e.g. a solid or liquid diluent), a pharmaceutically acceptable Possible adjuvants (eg surfactants), in particular pharmaceutically acceptable excipients and/or pharmaceutically acceptable adjuvants commonly used in veterinary preparations.

A related aspect of the present invention comprises mixing at least one compound of formula (I) with a pharmaceutically acceptable excipient and/or adjuvant, in particular a pharmaceutically acceptable excipient and/or adjuvant commonly used in veterinary formulations. A method for preparing a veterinary formulation as described herein, comprising.

Another particular aspect of the present invention, according to the aspect mentioned, is a further more selected from the group of ectoparasitic agents, and endoparasitic agents, more particularly selected from the group of anthelmintic, antiprotozoal, arthropod preparations. Veterinary preparations, in particular selected from the group of nematocides, miticides, acaricides or acaricides, insecticides and acaricides, and their methods for their preparation.

Another embodiment is to apply an effective amount of a compound of formula (I) to an animal, particularly a non-human animal, in need thereof to treat a parasitic infection, in particular an infection caused by a parasite selected from the group of ectoparasites and endoparasites referred to herein. It is about a method for the treatment of.

Another embodiment is to apply a veterinary preparation as defined herein to an animal, in particular a non-human animal, in need thereof to treat parasitic infections, in particular by parasites selected from the group of ectoparasites and endoparasites referred to herein. It relates to methods for the treatment of resulting infections.

Another aspect relates to the use of a compound of formula (I) in the treatment of parasitic infections, in particular infections caused by parasites selected from the group of ectoparasites and endoparasites mentioned herein, in animals, particularly non-human animals. will be.

In the context of animal health or veterinary medicine, the term "treatment" includes prophylactic, prophylactic, and therapeutic treatment.

In a particular embodiment, mixtures of at least one compound of formula (I) with other active compounds, in particular endoparasitic and ectoparasitic agents, are provided for the veterinary field.

In the field of animal health, "mixture" means not only two (or more) different active compounds formulated in a joint formulation and applied correspondingly together, but also products comprising separate formulations for each active compound. means Thus, if more than two active compounds are to be applied, all active compounds may be formulated in a joint formulation or all active compounds may be formulated in separate formulations; It is also a mixed form in which some of the active compounds are formulated together and some of the active compounds are formulated separately. Separate formulations permit separate or sequential applications of the active compounds in question.

The active compounds specified herein by their common names are known and are described, for example, in the "Pesticide Manual" (see above), or on the Internet (eg http://www.alanwood.net/pesticide ) can be found.

As mixing partners, exemplary active ingredients from the group of ectoparasitic agents include, without limitation, the insecticides and acaricides listed in detail above. Additional active ingredients that may be used are listed below according to the above-mentioned classification based on the current IRAC mode of action classification system: (1) acetylcholinesterase (AChE) inhibitors; (2) GABA-gated chloride channel blockers; (3) sodium channel modulators; (4) nicotinic acetylcholine receptor (nAChR) competitive modulators; (5) nicotinic acetylcholine receptor (nAChR) allosteric modulators; (6) a glutamate-gated chloride channel (GluCl) allosteric modulator; (7) juvenile hormone mimetics; (8) other non-specific (multisite) inhibitors; (9) chordal organ modulators; (10) mite growth inhibitors; (12) inhibitors of mitochondrial ATP synthase, such as ATP disruptors; (13) uncoupler of oxidative phosphorylation through disruption of the proton gradient; (14) nicotinic acetylcholine receptor channel blockers; (15) chitin biosynthesis inhibitors, type 0; (16) chitin biosynthesis inhibitors, type 1; (17) molting disruptors (particularly in the case of diptera, i.e., flies); (18) ecdysone receptor agonists; (19) Octopamine receptor agonists; (21) mitochondrial complex I electron transport inhibitor; (25) mitochondrial complex II electron transport inhibitor; (20) mitochondrial complex III electron transport inhibitor; (22) voltage-dependent sodium channel blockers; (23) inhibitors of acetyl CoA carboxylase; (28) ryanodine receptor modulators; (30) Allosteric modulators of GABA-gated chloride channels.

Active compounds with unknown or non-specific mechanisms of action, for example fentripanil, fenoxacrim, cycloprene, chlorobenzilate, chlordimeform, flubenzimine, dicyclanil, amidoflumet, quinome Thionate, triaraten, clothiazoben, tetrasul, potassium oleate, petroleum, methoxadiazone, gosiflur, flutenzine, bromopropylate, cryolite;

Other classes of compounds such as butacarb, dimethylane, cloethocarb, phosphocarb, pyrimiphos(-ethyl), parathion(-ethyl), methacryphos, isopropyl o-salicylate, trichlorphone , tigolaner, sulprophos, propafos, cebuphos, pyridathion, protoate, dichloropenthione, demeton-S-methylsulfone, isazophos, cyanofenphos, diallipos, carbophenothi one, autathiophos, aromphenvinphos (-methyl), azinphos (-ethyl), chlorpyrifos (-ethyl), fosmethylan, iodofenphos, dioxabenzophos, formothion, phonophos, flupyrazophos, phensulfothion, etrimphos;

organochlorine compounds such as camphechlor, lindane, heptachlor; or phenylpyrazoles such as acetoprole, pyrafluprole, pyriprole, vaniliprole, cisapronil; or an isoxazoline such as sarolaner, apoxolaner, rotilaner, fluralaner;

Pyrethroids such as (cis-, trans-), metoflutrin, profluthrin, flufenprox, flubrocitrinate, foubfenprox, fenfluthrin, protryfenbut, pyresmethrin , RU15525, teralethrin, cis-resmethrin, heptafluthrin, bioethanomethrin, biopermethrin, phenpyrithrin, cis-cypermethrin, cis-permethrin, clocitrin, cyhalothrin (lambda-) , clovaportrin, or halogenated hydrocarbon compounds (HCH),

neonicotinoids such as nithiazine

Dichloromesothiaz, Triflumezopyrim

macrocyclic lactones such as nemadectin, ivermectin, latidectin, moxidectin, selamectin, eprinomectin, doramectin, emamectin benzoate; milbemycin oxime

tryprene, epofenonane, diophenolane;

Biologics, hormones or pheromones such as natural products such as thuringiensin, codemones or neem components

dinitrophenols such as dinocap, dinobuton, binapacryl;

benzoylureas such as fluazuron, fenfluron,

Amidine derivatives such as chlormebuform, cymiazole, demiditraz

Honeycomb varroa acaricides, eg organic acids, eg formic acid, oxalic acid.

As a mixing partner, exemplary active ingredients from the group of endoparasitic agents include, without limitation, anthelmintic active ingredients and antiprotozoal active ingredients.

Parasiticidal active ingredients include, without limitation, the following nematicides, anthelmintic and/or tapeworm active ingredients:

from the class of macrocyclic lactones, for example: eprinomectin, abamectin, nemadectin, moxidectin, doramectin, selamectin, lepimectin, latidectin, milbemectin, ivermectin, emamectin, milbemycin;

from the class of benzimidazoles and probenzimidazoles, for example: oxybendazole, mebendazole, triclabendazole, thiophanate, parbendazole, oxfendazole, metobimin, fenbendazole, febantel, thiabendazole, cyclobendazole, cambendazole, albendazole-sulfoxide, albendazole, flubendazole;

from the class of depsipeptides, preferably cyclic depsipeptides, in particular 24-membered cyclic depsipeptides, for example: emodepsid, PF1022A;

from the class of tetrahydropyrimidines, for example: morantel, pyrantel, oxantel;

from the imidazothiazole class, for example: butamisole, levamisole, tetramisole;

from the aminophenylamidine class, eg: amidantel, deacylated amidantel (dAMD), tribendymidine;

from the class of aminoacetonitrile, for example: monepantel;

derived from parahercuamide enrichment, for example: parahercuamide, derquantel;

from the class of salicylanilides, for example: tribromsalan, bromoxanide, brothianide, cloxanide, closantel, niclosamide, oxyclozanide, rafoxanide;

from the class of substituted phenols, for example: nitroxynil, bithionol, disophenol, hexachlorophene, niclophoran, meniclophoran;

from the class of organophosphates, for example: trichlorphone, naphthalofos, dichlorvos/DDVP, cruformate, coumaphos, haloxone;

from the piperazinone/quinoline class, for example: praziquantel, epsiprantel;

from the piperazine class, for example: piperazine, hydroxyzine;

from the tetracycline class, eg: tetracycline, chlorotetracycline, doxycycline, oxytetracycline, rolitetracycline;

from various other classes, such as: bunamidine, niridazole, resorantel, omphalotin, oltipraz, nitroscanate, nitroxynil, oxamniquin, mirasan, miracil, leukantone, Hycanthone, hetolin, emetine, diethylcarbamazine, dichlorophen, diampenetide, clonazepam, bepenium, amoscanate, clorsulone.

Antiprotozoal active compounds include, without limitation, the following active compounds:

from the triazine class, for example: diclazuril, ponazurill, lettrazurill, toltrazuril;

from the class of polyether ionophores, for example: monensin, salinomycin, maduramicin, naracin;

from the class of macrocyclic lactones, for example: milbemycin, erythromycin;

from the class of quinolones, for example: enrofloxacin, pradofloxacin;

from the quinine class, for example: chloroquine;

from the pyrimidine class, for example: pyrimethamine;

from the class of sulfonamides, for example: sulfaquinoxaline, trimethoprim, sulfaclozine;

from the thiamine class, for example: Amprollium;

from the lincosamide class, for example: clindamycin;

from the class of carbanilides, for example: imidocarb;

from the nitrofuran class, for example: Nifurtimox;

from the class of quinazolinone alkaloids, for example: halofuginone;

from various other classes, such as: oxamniquin, paromomycin;

Microorganisms, for example: Babesia canis rossi, Eimeria tenella, Eimeria praecox, Eimeria necatrix, Eimeria mytis (Eimeria mitis), Eimeria maxima, Eimeria brunetti, Eimeria acervulina, Babesia canis vogeli, Leishmania infantum (Leishmania infantum), Babesia canis canis, Dictyocaulus viviparus Antigen or vaccine class derived.

All named mixing partners are optionally capable of forming salts with suitable bases or acids, provided their functional groups allow this.

vector control

The compounds of formula (I) can also be used in vector control. For the purposes of the present invention, a vector is an arthropod, in particular an insect or arachnid, capable of transmitting pathogens such as, for example, viruses, parasites, unicellular organisms and bacteria from a reservoir (plant, animal, human, etc.) to a host. . Pathogens can be transmitted from the host to the host mechanically (eg trachoma by stingless flies) or via injection (eg malaria parasites by mosquitoes).

Examples of vectors and the diseases or pathogens they transmit are:

1) Mosquito

- Anopheles: malaria, filariasis;

- Culex: transmission of Japanese encephalitis, other viral diseases, filariasis, and other parasites;

- Aedes: yellow fever, dengue fever, other viral diseases, filariasis;

- Simuliidae: transmission of parasites, especially Onchocerca volvulus;

- Psychodidae: transmission of leishmaniasis

2) Lice: skin infections, typhus typhus;

3) Fleas: plague, endemic typhus, tapeworm;

4) Flies: sleeping sickness (trypanosomiasis); cholera, other bacterial diseases;

5) Ticks: mite, typhus, rickettsial pox, wild rabbit disease, St. Louis encephalitis, tick-borne encephalitis (TBE), Crimean-Congo hemorrhagic fever, borreliosis;

6) Ticks: Borellioses such as Borrelia burgdorferi sensu lato., Borrelia duttoni, tick-borne encephalitis, Q fever (Coxiella burnetii)), babesiosis (Babesia canis canis), ehrlichosis.

Examples of vectors in the sense of the present invention are insects, such as aphids, flies, leafhoppers, or thrips, capable of transmitting plant viruses to plants. Other vectors that can transmit plant viruses are spider mites, beetles and nematodes.

Further examples of vectors in the sense of the present invention are insects and arachnids, such as mosquitoes, in particular of the genera Aedes, Anopheles, capable of transmitting pathogens to animals and/or humans, eg A. Gambiae (A. gambiae), A., Arabiensis (A. arabiensis), A., funestus (A. funestus), A. A. dirus (malaria) and Culex, psychodids such as Phlebotomus, Lutzomyia, lice, fleas, flies, ticks and ticks.

Vector control is also possible if the compound of formula (I) is resistance-breaking.

The compounds of formula (I) are suitable for use in the prevention of vector-borne pathogens and/or diseases. A further aspect of the present invention is therefore the use of compounds of formula (I) for vector control, for example in agriculture, horticulture, gardens and leisure facilities, and also in the protection of materials and stored products.

Protection of industrial materials

The compounds of formula (I) are effective against, for example, insects from the order Coleoptera, Hymenoptera, Isoptera, Lepidoptera, Psocoptera and Zygentoma. It is suitable for protecting industrial materials against attack or destruction by

Industrial materials in this context are understood to mean inanimate materials, such as preferably plastics, adhesives, sizes, paper and card, leather, wood, engineered wood products and coating compositions. The use of the present invention for protecting wood is particularly preferred.

In a further embodiment, the compound of formula (I) is used in combination with at least one additional insecticide and/or at least one fungicide.

In a further embodiment, the compounds of formula (I) are present as ready-to-use agrochemicals, ie they can be applied to the subject matter without further modification. Suitable further insecticides or fungicides include in particular those mentioned above.

Surprisingly, it has also been found that the compounds of formula (I) can be applied to protect objects coming into contact with salt or brackish water, in particular hulls, screens, buildings, moorings and signaling systems from fouling. Similarly, the compounds of formula (I) may be used alone or in combination with other active compounds as antifouling agents.

Control of pests in the hygiene sector

The compounds of formula (I) are suitable for controlling pests in the sanitary sector. In particular, the present invention relates to the control of insects, arachnids, mites and mites encountered in the household sector, in the hygiene sector and in the protection of stored products, in particular in confined spaces such as houses, factory halls, offices, garages and animal rooms. can be applied for For the control of pests, the compounds of formula (I) are used alone or in combination with other active compounds and/or adjuvants. They are preferably used in household pesticide products. The compounds of formula (I) are effective against sensitive and resistant species and against all stages of development.

These pests are, for example, from the class Arachnids, from the order Scorpions, from the order Arachnoids, and from the order Arachnids, from the classes Centipedes and Millipedes, from the class Insects, from the order Cockroaches, from the order Chiroptera, from the order Diptera, stink bugs, It includes pests from the order Maxima, Termites, Lepidoptera, Diptera, Pterodactyl, Orchiptera or Locust, Flea, and Zombie, as well as from the softshell Orbital.

They include, for example, aerosols, pressurized spray products such as pump and atomizer sprays, automatic misting systems, nebulizers, foams, gels, evaporator products with evaporator tablets made of cellulose or plastics, liquid evaporators, gels and films. Used as evaporators, propeller-driven evaporators, energyless or manual evaporation systems, moth paper, moth bags and moth gels, as granules or dust, in spreading baits or bait houses.

Abbreviations and Symbols

AcOH: acetic acid

aq.: Mercury

br.: extensive

d: double term

DABCO 1,4-diazabicyclo[2.2.2]octane

DCC: N,N'-dicyclohexylcarbodiimide

DCM: dichloromethane

DIPEA: N,N-diisopropylethylamine

DMF: N,N-dimethylformamide

DMSO: Dimethylsulfoxide

ee: Enantiomeric excess

eq.: equivalent weight

ES: electrospray ionization

Et ₃ N triethylamine

EtOAc: ethyl acetate

h(rs) time(s)

HATU: 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridium-3-oxide hexafluorophosphate

HOBt: 1-hydroxybenzotriazole hydrate

HPLC: High Performance Liquid Chromatography

i PrOH: isopropanol

J : binding constant

LCMS: Liquid Chromatography-Mass Spectrometry

m/z : mass-to-charge ratio

M: molarity

m: polynomial

MeCN acetonitrile

MeOH: methanol

NaH ₂ PO ₄ monosodium phosphate

NaOH sodium hydroxide

Na ₂ SO ₄ sodium sulfate

NH ₄ Cl ammonium chloride

NMR: nuclear magnetic resonance

q: quartet

r. t.: room temperature

R _t : residence time

s: single term

sat.: saturation

T: Temperature

t: triplet

T3P ^® : Propylphosphonic anhydride

THF: tetrahydrofuran

TMSOK Potassium Trimethylsilanolate

wt.: weight

Zantfoss: 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene

δ: chemical shift

λ: wavelength

Description of process and intermediates

Compounds of formula (I′) can be prepared as illustrated in the scheme below, wherein R ¹ , R ² , R ³ and R ⁴ are as previously defined and X ¹ represents OH or Cl.

Scheme 1

X ¹ = OH: A triazole compound of formula (1) is reacted with a carboxylic acid of formula (2a) (X ¹ = OH) to form a compound of formula (I′). For example, a triazole of formula (1) in a suitable solvent such as ethyl acetate or DMF, a carboxylic acid of formula (2a) (X ¹ = OH), a suitable coupling reagent such as T3P ^® , HATU or DCC/HOBt , a mixture of a suitable base such as triethylamine or DIPEA can be mixed at a temperature ranging from about 0 to 100° C. to give a compound of formula (I′), which can then be isolated and, if necessary and desired, well known in the art. It can be purified using known techniques, such as chromatography.

X ¹ = Cl: A compound of formula (1) is reacted with a carboxylic acid chloride of formula (2b) (X ¹ = Cl) to form a compound of formula (I′). For example, a mixture of a triazole of formula (1), a carboxylic acid chloride (X ¹ =Cl) of formula (2b), a suitable base such as triethylamine or DIPEA in a suitable solvent such as dichloromethane or THF is about Mixing at a temperature in the range of 0 to 100° C. provides a compound of formula (I′) which can then be isolated and, if necessary and desired, purified using techniques well known in the art, such as chromatography.

Thioamides of formula (I), where X = S, can be obtained by treating compounds of formula (I') with Lawesson's reagent in boiling toluene, as described for example in WO 2005009435.

The carboxylic acid of formula (2a) (X ¹ =OH) and the carboxylic acid chloride of formula (2b) (X ¹ =Cl) are commercially available or can be synthesized by methods known to those skilled in the art. The synthesis of certain carboxylic acids of formula (2a) (X ¹ =OH) is described in WO 2019/197468.

3-[(1,1,2,2-tetrafluoroethyl)sulfanyl]benzoic acid: The synthesis is [J. Org. Chem. 1964, vol 29, 895-898. An alternative synthesis is possible starting with 3-sulfanylbenzoic acid, the latter converted to the methyl ester using HCl in MeOH, followed by 1,2-dibromo-1 at 60 °C in the presence of cesium carbonate in DMSO. Alkylated with ,1,2,2-tetrafluoroethane. The resulting methyl 3-[(2-bromo-1,1,2,2-tetrafluoroethyl)sulfanyl]benzoate is debrominated with Zn in AcOH at 50°C. Hydrolysis of the methyl ester yields 3-[(1,1,2,2-tetrafluoroethyl)sulfanyl]benzoic acid.

A compound of formula (1) can be prepared as illustrated in Scheme 2 below, wherein R ¹ and R ³ are as previously defined and R ⁴ is hydrogen or C ₁ -C ₃ alkyl.

Scheme 2

An amide of formula (3) is reacted with N , N -dimethylamide dimethyl acetal of formula (4) to form a compound with formula (5) followed by a substituted hydrazine of formula (6) or a suitable salt thereof (for example , hydrochloric acid salt) under acidic conditions to form the compound of formula (7). For example, a compound of formula (3) and N , N -dimethylamide dimethyl acetal of formula (4) are reacted at reflux in a suitable solvent such as CH ₂ Cl ₂ to give a compound of formula (5). After removal of the solvent, the compound of formula (5) is mixed with a substituted hydrazine of formula (6) or a suitable salt thereof (eg a hydrochloric acid salt) with a suitable solvent such as 1,4-dioxane, acetic acid or mixtures of such solvents. reacted at a temperature in the range of about 20 to 80 ° C. The final compound of formula (7) can then be isolated and, if necessary and desired, purified using techniques well known in the art, such as chromatography.

Carbamates of formula (7) are treated with acids to form amines of formula (1). For example, the carbamate of formula (7) and a suitable acid, such as hydrogen chloride or trifluoroacetic acid, can be mixed in a suitable solvent, such as 1,4-dioxane or without additional solvent in the case of trifluoroacetic acid, at approximately 0 to 80° C. React at a range of temperatures. The final amines of formula (1) can then be isolated as their acid salts or as free amines after base treatment and, if necessary and desired, purified using techniques well known in the art, such as chromatography.

The requisite amides of formula (3) and hydrazines of formula (6) or suitable salts thereof (e.g., hydrochloric acid salts) are commercially available or can be synthesized via methods described herein or methods known to those skilled in the art. there is.

For example, hydrazine of formula (6) can be obtained as follows:

6-Hydroxypyrimidine-4-carboxylic acid is [J. Org. Chem. 1961, 2755]; WO2010/20432 A2; It is obtained as described in US2011/21500 A1 or US2007/259860 A1 and converted to 6-chloropyrimidine-4-carbonyl chloride analogously to WO2010/20432 A2. The acid chloride functionality of the latter is then converted to an amide by reaction at 0° C. with an appropriate amine in a solvent such as THF. If the reacted amine is different from ammonia, only 1 equivalent of the reacted amine is used and a suitable base such as triethyl amine is additionally used. Amides of this type are known from [Chemistry of heterocyclic compounds 1972, vol8, p509]. Finally, the chloropyrimidine functionality is converted to hydrazinopyrimidines by reacting with hydrazine hydrate in a solvent such as methanol at RT or at elevated temperatures up to 65°C, similar to [Ukrainskii Khimicheskii Zhurnal 1982, 48(1), 67-69]. do.

Compounds of formula (I′) may alternatively be prepared as illustrated in Scheme 3 below, wherein R ¹ , R ² , R ³ and R ⁴ are as previously defined and R ⁵ is hydrogen or C ₁ -C ₃ alkyl.

Scheme 3

The amide of formula (8) is reacted with N , N -dimethylamide dimethyl acetal of formula (4) to form a compound of formula (9), followed by a substituted hydrazine of formula (6) or a suitable salt thereof (eg eg, a hydrochloric acid salt) under acidic conditions to form a compound of formula (I′). For example, a compound of formula (8) and N , N -dimethylamide dimethyl acetal of formula (4) are reacted at reflux in a suitable solvent such as CH ₂ Cl ₂ to give a compound of formula (9). Upon removal of the solvent, the compound of formula (9) is mixed with a substituted hydrazine of formula (6) or a suitable salt thereof (eg, a hydrochloric acid salt) with a suitable solvent such as 1,4-dioxane, acetic acid or mixtures of such solvents. reacted at a temperature in the range of about 20 to 100 ° C. The final compound of formula (I′) can then be isolated and, if necessary and desired, purified using techniques well known in the art, such as chromatography.

The requisite hydrazine of formula (6) or a suitable salt thereof (eg, hydrochloric acid salt) is commercially available or can be synthesized via methods described herein or methods known to those skilled in the art.

The essential amide of formula (8) can be prepared as illustrated in Scheme 4 below, wherein R ¹ and R ² are as previously described (see also WO 2017/192385).

Scheme 4

An amino amide of formula (10) reacts with a carboxylic acid of formula (2a) (X ¹ =OH) to form a compound of formula (8). For example, an amino amide of formula (10), a mixture of carboxylic acid (2a) (X ¹ =OH), a suitable coupling reagent such as T3P ^® , HATU or DCC/HOBt, a suitable base such as triethylamine or DIPEA in a suitable solvent such as ethyl acetate or DMF at a temperature in the range of approximately 0 to 100° C. to provide a compound of formula (8), which can thereafter be isolated and, if necessary and desired, well known in the art. It is purified using techniques such as chromatography.

Alternatively, an amino amide of formula (10) is reacted with a carboxylic acid chloride (X ¹ =Cl) of formula (2b) to form a compound of formula (8). For example, a mixture of an amino amide of formula (10), a carboxylic acid chloride of formula (2b) (X ¹ =Cl), a suitable base such as triethylamine or DIPEA, in a suitable solvent such as dichloromethane or THF, Mixing at a temperature ranging from about 0 to 100° C. provides a compound of formula (8) which can then be isolated and, if necessary and desired, purified using techniques well known in the art, such as chromatography.

Compounds of formula (10) are commercially available or can be synthesized through methods known to those skilled in the art. The carboxylic acid of formula (2a) (X ¹ =OH) and the carboxylic acid chloride of formula (2b) (X ¹ =Cl) are commercially available or can be synthesized through methods known to those skilled in the art. The synthesis of certain carboxylic acids of formula (2a) (X ¹ =OH) is described in WO 2019/197468.

Scheme 5 illustrates the preparation of alkyltriazole and cycloalkyltriazole containing amines (1a), wherein R ⁴ is C ₁ -C ₃ alkyl or C ₃ -C ₄ cycloalkyl. Z is NH ₂ or OC ₁ -C ₆ alkyl.

Scheme 5

N-(tert-butoxycarbonyl)-alanine (3a) is reacted with an alkylamidine (11a, Z = NH ₂ ) or an alkylimidate (11b, Z = OC ₁ -C ₆ alkyl) to form formula (12) and subsequently reacted with a substituted hydrazine of formula (6) to form an alkyltriazole of formula (7a).

N-(tert-butoxycarbonyl)-alanine and formula (11a) for example (11a, Z = NH ₂ ) (compare [ J. Org. Chem . 2011, 76, 1177-1179]) The alkylamidine of is reacted in the presence of a suitable coupling reagent such as HATU, a suitable base such as triethylamine or DIPEA in a suitable solvent such as DMF at a temperature ranging from 0 to 50° C. to form an acylamide of formula (12) Dean intermediates are formed. After removal of the solvent, the intermediate of formula (12) is reacted with a substituted hydrazine of formula (6) or a suitable salt thereof (eg, a hydrochloric acid salt) in a suitable solvent such as acetic acid at a temperature ranging from approximately 20 to 80 °C. . The final alkyltriazole of formula (7a) can then be isolated and, if necessary and desired, purified using techniques well known in the art, such as chromatography.

N-(tert-butoxycarbonyl)-alanine in the case of Z = OC ₁ -C ₆ alkyl and an alkylimidate of formula (11b) or a suitable salt thereof are combined with a suitable coupling reagent such as HATU, a suitable base such as triethyl In the presence of an amine or DIPEA in a suitable solvent such as THF at a temperature ranging from approximately 0 to 25° C. to form an acyl imidate intermediate of formula (12b). Upon addition of the substituted hydrazine of formula (6) or a suitable salt thereof (eg, a hydrochloric acid salt), the intermediate of formula (12b) reacts at a temperature in the range of approximately 20 to 80 °C to form an alkyltria of formula (7a). The sol is provided and can then be isolated and, if necessary and desired, purified using techniques well known in the art, such as chromatography.

Carbamates of formula (7a) are treated with acids to form amines or associated salts of formula (Ia) as described in Scheme 2 for amines of formula (1).

The requisite alkylamidines (11a) and alkylimidates (11b) or suitable salts thereof and hydrazines of formula (6) or suitable salts thereof (eg, hydrochloric acid salts) are commercially available or by the methods described herein. or can be synthesized by methods known to those skilled in the art (eg see WO 2011/133447 for the synthesis of methyl cyclopropanecarboxymidate hydrochloride).

Compounds of formula (1b), wherein alkyl is C ₁ -C ₃ alkyl and R ³ is as previously defined, can be prepared as illustrated in Scheme 6 below.

Scheme 6

2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoic acid and oxalyl chloride according to [ Tetrahedron: Asymmetry, 21(8), 936-942, 2010] 2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoyl chloride (13), prepared from The corresponding isocyanate intermediate (14) was obtained by treatment with the corresponding alcohol (alkylOH) in the next step to O-alkyl [2-(1,3-dioxo-1,3-dihydro-2H-isoindole-2 -yl)propanoyl]carbamothioate (15). The reaction between the intermediate of formula (15) and the hydrazine of formula (6) or its hydrohalic acid salt in ethanol is cyclization of formula (16) as described in [Bioorganic & Medicinal Chemistry 26 (2018) 3321-3344]. provide a product that is In a final step, the phthalimide protecting groups are removed by reaction with hydrazine hydrate in a suitable solvent such as ethanol, as described in WO 2018/086605. The obtained amine (1b) is then reacted with a carboxylic acid as described in Scheme 1 to form an example compound.

A compound of formula (21) can be prepared as illustrated in Scheme 7 below, wherein E is H or C ₁ -C ₆ alkyl, Hal is bromine or iodine, and R ²² is as previously described; G is cyclopropyl, wherein cyclopropyl is optionally substituted with 1 to 2 substituent(s) selected from the group of halogen, -CN, methyl or trifluoromethyl.

Scheme 7

A halogen-containing compound of formula (19) is reacted with a boronic acid of formula (20) or the corresponding boronic acid ester to form a compound of formula (21). For example, tricyclohexylphosphine, a halogen-containing compound of formula (19) in combination with a suitable base such as tripotassium phosphate, a boronic acid (20), a mixture of a suitable catalyst such as palladium(II) acetate, in a suitable solvent or Reacting in a solvent mixture such as toluene and water at a temperature in the range of approximately 0 to 100° C. provides a compound of formula (21) which can then be isolated and, if necessary and desired, by techniques well known in the art, such as chromatography. refined using graphs. A compound of formula (21), wherein E is C ₁ -C ₆ alkyl, is treated with an alkali hydroxide in a suitable solvent or solvent mixture such as /containing tetrahydrofuran, ethanol or water at a temperature ranging from about 0 to 100 °C. to a compound of formula (21) wherein E is H.

A compound of formula (23) can be prepared as illustrated in Scheme 8 below, wherein E is H or C ₁ -C ₆ alkyl, Hal is iodine or bromine, and Ra is C ₁ -C ₃ alkyl or syl. propyl, and R ²² is as previously described.

Scheme 8

An allyl halide of formula (20) reacts with a sulfinate salt of formula (22) under a copper salt catalysis to form a sulfone of formula (23).

For example, a mixture of a compound of formula (20), sodium sulfinate salt of formula (22), copper(I) iodide, proline and sodium hydroxide in a suitable solvent such as dimethyl sulfoxide at 40 to 140° C. It reacts at a temperature in the range (compare WO 2019/197468). In an alternative approach, a mixture of a compound of formula (20), sodium sulfinate salt of formula (22), copper(I) iodide, trans- N,N -dimethylcyclohexane-1-2-diamine and cesium carbonate is reacted at a temperature ranging from 40 to 140° C. in a suitable solvent such as DMF.

The final compound of formula (23) can then be isolated and, if necessary and desired, purified using techniques well known in the art, such as chromatography. Compounds of formula (23), wherein E is C ₁ -C ₆ alkyl, can be obtained by treatment with an alkali hydroxide in a suitable solvent or solvent mixture such as / containing tetrahydrofuran, ethanol or water at a temperature ranging from about 0 to 100 ° C. It can be converted to a compound of formula (23) wherein E is H. When E is a tert-butyl group, these esters can be cleaved in the presence of a suitable acid such as trifluoroacetic acid in a suitable solvent such as dichloromethane under acidic conditions at temperatures ranging from 0 - 40°C.

Aryl halides (20) and sulfinate salts of formula (22) are commercially available or can be synthesized through methods known to those skilled in the art.

In an alternative approach, a compound of formula (23a) can be prepared as illustrated in Scheme 9a below, wherein Hal is fluorine or chlorine, Ra is C ₁ -C ₃ alkyl or syllopropyl, and R ²² is previously As described.

Scheme 9a

An allyl halide of formula (24) reacts with a thiolate salt of formula (25) to form a thioether of formula (26) which is then hydrolyzed to form a carboxylic acid of formula (27). In a third step, the thioether of formula (27) is oxidized to a sulfone of formula (23a).

For example, a mixture of a halide of formula (24) and sodium thiolate of formula (25) is reacted in a suitable solvent such as N,N-dimethylformamide at a temperature in the range of -20 to 50 °C. The final nitrile of formula (26) is then prepared under basic conditions, for example using aqueous sodium hydroxide in a suitable solvent or solvent mixture such as isopropanol or methanol/THF, at a temperature ranging from 40 to 100° C. or with a suitable diluent such as It is diluted with water or hydrolyzed neatly at a temperature in the range of 40 to 100° C. under acidic conditions of a suitable strong acid such as sulfuric or hydrochloric acid. The carboxylic acid 27 obtained is then, if necessary and desired, purified using techniques well known in the art, such as chromatography (also 3-chloro-5- See US 20060276536 for synthesis of (difluoromethyl)benzoic acid and acidic hydrolysis conditions).

A thioether-containing compound of formula (27) is reacted with an oxidizing agent such as a combination of 3-chloroperoxybenzoic acid or formic acid and hydrogen peroxide in a suitable solvent such as dichloromethane at a temperature ranging from 0 to 50° C. to form a sulfone of formula (23). . The obtained sulfone of formula (23a) is then purified, if necessary and desired, using techniques well known in the art, such as chromatography.

The requisite aryl halides (24) and thiolate salts of formula (25) are either commercially available or can be synthesized by methods known to those skilled in the art (see, for example, WO 2013/049250 for the synthesis of cyclopropanethiol). . Thiolate salts can be synthesized from the corresponding thiols via deprotonation with sodium hydride in a suitable solvent such as N,N-dimethylformamide.

In a further alternative approach, compounds of formula (23b) can be prepared as illustrated in Scheme 9b below, wherein Hal is chlorine, bromine or iodine and Ra is C ₁ -C ₃ alkyl or C ₁ -C ₃ haloalkyl, and R ²² is as previously described.

Scheme 9b

Dibromobenzene of formula (43) can be lithiated in the presence of a lithium transfer reagent, such as n-butyllithium, at low temperatures in the range of -78 to 0 °C, as described in WO2009148052, followed by sulfur can react with Thiols of final formula (45) can be prepared in the presence of a base and in the case of CF ₃ Hal a phase transfer catalyst such as 1,1'-dimethyl-[4,4'-bipyridine]-1,1'-diium di It can be alkylated with an alkylating reagent (46) in the presence of chloride.

The final sulfane of formula (47) can be carbonylated and subsequently oxidized via methods known to those skilled in the art to give the sulfone of formula (23b).

Compounds of formula (34) can be prepared as illustrated in Scheme 10 below. R _f is C ₁ -C ₃ haloalkyl and R ²¹ is as previously described. Hal is iodine or chlorine when R _f is difluoromethyl. When R ²¹ is iodine or bromine, it can be converted to an optionally substituted cyclopropyl as described in Scheme 7.

Scheme 10

The aryl fluoride of formula (28) reacts with sodium sulfide (29) to form a thiol of formula (30) as described, for example, in Tetrahedron Letters , 2012, 53(20), 2548-2551. Subsequently, a haloalkylthioether (32) is formed under alkylating conditions, for example using a haloalkyliodide or difluoromethylchloride and a suitable base. In the case of trifluoromethyliodide additional catalysts are used, for example as described in WO 2015035223. The nitrile functionality is then hydrolyzed to form the carboxylic acid of formula (33). In a further step, the thioether of formula (33) is oxidized to a sulfone of formula (34).

For example, a mixture of aryl fluoride of formula (28) and sodium sulfide (29) is reacted in a suitable solvent such as N,N-dimethylformamide at a temperature in the range of -20 to 50 °C. The thiol of the final formula (30 is then prepared in a suitable solvent such as N,N-dimethylformamide, for example -20 in the presence of triethylamine and 1,1'-dimethyl-4,4'-bipyridium dichloride. to 50° C., alkylation with trifluoromethyl iodide.

The obtained thioether of formula (32) is diluted using aqueous sodium hydroxide in a suitable solvent such as methanol, under basic conditions at a temperature ranging from 40 to 100° C. or with a suitable diluent such as water, or diluted neat with a suitable strong acid such as It is hydrolyzed at temperatures ranging from 40 to 100° C. under acidic conditions in sulfuric or hydrochloric acid. The carboxylic acid 33 obtained is then, if necessary and desired, purified using techniques well known in the art, such as chromatography.

A thioether-containing compound of formula (33) is reacted with an oxidizing agent such as 3-chloroperoxybenzoic acid or a combination of acetic acid and hydrogen peroxide in a suitable solvent such as dichloromethane at a temperature ranging from 0 to 50° C. to form a sulfone of formula (34). . The obtained sulfone of formula (34) is then, if necessary and desired, purified using techniques well known in the art, such as chromatography.

The requisite aryl fluoride (28) is commercially available or can be synthesized through methods known to those skilled in the art.

In an alternative approach an acid of formula (38) containing a substituted cyclopropyl group can be prepared as illustrated in Scheme 11 below, wherein R ²² is as previously described and Z ¹ is -CN or -CO ₂ C ₁ -C ₆ alkyl. Z ² and Z ³ are independently selected from the group of hydrogen, halogen, —CN, methyl or trifluoromethyl, provided that only at most three of the substituents Z ² and Z ³ are different from hydrogen. L is iodine or trifluoroacetate. M is a transition metal complex fragment containing iron, copper, palladium or rhodium and suitable ligand substitutions.

Scheme 11

Alkene-containing compounds of formula (35) react with free carbene (36a), zinc carbenoids (36c) and certain transition metal carbene complexes (36b) to give cyclopropyl-containing compounds of formula (37). These can then be converted to acids of formula (38) by ester cleavage (if Z ¹ is -CO ₂ C ₁ -C ₆ alkyl) or hydrolysis of the cyano group (if Z ¹ is -CN). Different cyclopropanation reactions are known to those skilled in the art and have been reviewed in the literature (see eg [ Chem. Rev. 2017, 117, 11651 - 11679]).

In the case of reaction with zinc carbenoids (36c), zinc carbenoids are formed upon first reacting Et ₂ Zn with trifluoroacetic acid in a suitable solvent such as anhydrous dichloromethane at 0° C. followed by addition of CH ₂ I ₂ . Upon addition of the alkene 35, the preformed zinc carbenoid reacts with the alkene at a temperature in the range of 20 - 40°C to form cyclopropane (see also WO 2012/139775).

Different transition metal carbene complexes (36b) have been found suitable for cyclopropanation reactions. Examples of suitable precursors for these complexes are CuBr, Pd(OAc) ₂ , Rh(OAc) ₄ or iron(III)-5,10,15,20-tetraphenyl-porphyrin (Fe(TPP)Cl).

In the case of the reaction via the palladium carbene complex, a solution of the alkene (35) in a suitable solvent such as tetrahydrofuran or diethyl ether is prepared at a temperature in the range of 0 °C - 20 °C in the presence of a suitable palladium salt such as Pd(OAc) ₂ . with a solution of diazomethane in a solvent such as diethyl ether (see also WO 2014/023367). A trifluoromethyl substituted cyclopropyl group can be found in [ Angew. Chem. Int. Ed. 2010, 49, 938-941], it can be obtained through the reaction of an iron carbene complex obtained from trifluoromethyl diazomethane and Fe(TPP)Cl produced in situ with an alkene (35). there is.

In the case of reaction with free carbene 36a, a solution of alkene 35 in a suitable solvent is mixed with the carbene precursor from which free carbene is generated in situ. For example, a solution of alkene (35) in diglyme is heated in the presence of sodium bromo(difluoro)acetate at a temperature in the range of 60-80°C. An alternative carbene precursor is for example trimethyl(trifluoromethyl)silane used in combination with sodium iodide (as described in WO 2017/040742).

Final hydrolysis of the cyano group to the corresponding acid (38) can be carried out under basic or acidic conditions as described in Scheme 9. Hydrolysis of esters can be carried out as described in Scheme 8.

Reagents necessary for the production of the requisite alkenes (35) and free carbene (36a), zinc carbenoids (36c) and certain electrical metal carbene complexes (36b) are either commercially available or synthesized through methods known to those skilled in the art. It can be. For the synthesis of substituted alkenes (35) via a palladium catalyzed coupling reaction, see for example WO 2013/178362 (1-bromo-3-(1,1-dimethylethyl)-5-(1-methyl tenyl)benzene) and WO 2012/035011 (1,5-dichloro-2-fluoro-3-(3,3,3-trifluoropropyl-1-en-2-yl)benzene).

The following preparation and use examples illustrate the present invention without restricting it.

Scheme 12 illustrates the preparation of triazole-containing amine (1b), wherein R ⁴ , R ³¹ and R ³² are as previously described, Alk is C ₁ -C ₃ alkyl, and Hal is chlorine, bromine or iodine. do.

An intermediate of formula (5a) or (12) is reacted with a substituted hydrazine of formula (39) or a suitable salt thereof (eg, a hydrochloric acid salt) in a suitable solvent such as acetic acid at a temperature ranging from about 20 to 80 °C. . The final 4-halogen-pyrimidin-6-yl-triazole of formula (40) can then be isolated and, if necessary and desired, purified using techniques well known in the art, such as chromatography.

Subsequently, 4-halogen-pyrimidin-6-yl-triazoles of formula (40) can be prepared on palladium catalysts, for example, as described in WO 2012/035039, [1,1'-bis(diphenyl and pressurized with carbon monoxide in a suitable C ₁ -C ₃ alcohol such as methanol or ethanol in the presence of phosphino)ferrocene]dichloropalladium. The final ester of formula (41) can be converted to an amide of formula (42) via methods described herein or methods known to those skilled in the art.

Carbamates of formula (42) are treated with acids to form amines or associated salts of formula (1b) as described in Scheme 2 for amines of formula (1).

The requisite amidines (5a) and imidates (12) are described in Scheme 2 and Scheme 5, and hydrazines of formula (39) or suitable salts thereof (eg, hydrochloric acid salts) are commercially available or in the present application. It can be synthesized by the method described in or known to those skilled in the art.

Scheme 12

A compound of formula (53) can be prepared as illustrated in Scheme 13 below. R ²² is as previously described.

Scheme 13

The aryl bromide of formula (49) can be prepared from 1-hydroxy-1-methyl-ethyl aryl of formula (50) using Grignard reagents such as acetone and isopropyl magnesium chloride as electrophiles, as described in WO 2017/055859. easily converted into compounds. The final compound (50) can be carbonylated via methods known to those skilled in the art, followed by fluorination (fluorination: see e.g. Journal of Medicinal Chemistry (2019), 62(9), 4350-4369) and Hydrolysis gives benzoic acid of formula (52).

A compound of formula (59) can be prepared as illustrated in Scheme 14 below. R _f is C ₁ -C ₃ haloalkyl and LG describes a leaving group, eg chlorine, bromine, iodine or methyl sulfonate.

Scheme 14

Methyl 3,5-dimercaptobenzoate (57) can be readily prepared according to known procedures described in US 20020072583. Haloalkylation with R _f LG is described for example in WO 2004/007444 or with CF ₂ ClCO ₂ Na in WO 2020/002563. The final thioether compound (58) can be oxidized via methods known to those skilled in the art and subsequently hydrolyzed to give benzoic acid of formula (59).

manufacturing example

3-Bromo-N-{(1S)-1-[1-(6-cyanopyrimidin-4-yl)-1H-1,2,4-triazol-5-yl]ethyl}-5- Synthesis of (trifluoromethoxy)benzamide (Example I-1)

Step 1: 2 N-[(2S)-1-amino-1-oxopropan-2-yl]-3-bromo-5-(trifluoromethoxy)benzamide

1.75 g (14.0 mmol) of L-alaninamide-hydrochloride, 1.0 g (3.5 mmol) 3-bromo-5-(trifluoromethoxy)benzoic acid and 3.1 mL triethylamine were stirred in 10 mL DMF with ice-water cooling. did To the mixture was added 3.1 mL (5.3 mmol) of T3P (cyclic propanephosphonic anhydride) 50% in EtOAc. The mixture was stirred overnight at room temperature. Water was added to the reaction mixture and a white precipitate formed. The precipitate was isolated by filtration and dissolved in ethyl acetate. Dilute the solution with hydrochloric acid (10%), water and saturated aq. Washed successively with NaHCO ₃ solution and brine. Evaporation of the solvent gave 1.13 g N-[(2S)-1-amino-1-oxopropan-2-yl]-3-bromo-5-(trifluoromethoxy)benzamide.

ESI mass [m/z]: 355.0 [M+H] ⁺

Step 2: 3-Bromo-N-{(1S)-1-[1-(6-cyanopyrimidin-4-yl)-1H-1,2,4-triazol-5-yl]ethyl}-5- (trifluoromethoxy)benzamide (Example I-1)

of 160 mg (0.45 mmol) N-[(2S)-1-amino-1-oxopropan-2-yl]-3-bromo-5-(trifluoromethoxy)benzamide in 3 mL CH ₂ Cl ₂ To the solution was added 0.09 mL (0.67 mmol) N,N-dimethylformamide dimethylacetal. The solution was heated at reflux for 2 h after which time the solvent was removed under reduced pressure. The residue was dissolved in 3 mL glacial acetic acid. 93 mg (0.54 mmol) 6-hydrazinopyrimidine-4-carbonitrile hydrochloride were added and the mixture was stirred at 80° C. for 2 hours. Next, the solvent was removed under reduced pressure, and the residue was purified via reverse phase chromatography (water/acetonitrile) to give 159 mg of 3-bromo-N-{(1S)-1-[1-(6-cya) Nopyrimidin-4-yl)-1H-1,2,4-triazol-5-yl]ethyl}-5-(trifluoromethoxy)benzamide was provided.

1H ^- NMR (400 MHz, DMSO-d ₆ ): δ = 9.42 (d, J = 6.8 Hz, 1H), 9.38 (d, J = 1.2 Hz, 1H), 8.61 (d, J = 1.2 Hz, 1H) ), 8.36 (s, 1H), 8.14 (s, 1H), 7.90 (s, 1H), 7.80 (s, 1H), 6.22 - 6.13 (m, 1H), 1.63 (d, J = 6.8 Hz, 3H) .

ESI mass [m/z]: 484.1 [M+H] ⁺

N-{1-[1-(6-cyanopyrimidin-4-yl)-1H-1,2,4-triazol-5-yl]ethyl}-3-cyclopropyl-5-(trifluoromethyl) Synthesis of toxy)benzamide (Example I-8)

Step 1: 6-hydrazinopyrimidine-4-carbonitrile

A mixture of 500 mg (3.58 mmol) 6-chloropyrimidine-4-carbonitrile and 7.2 mL (7.2 mmol) of a 1 M solution of hydrazine in THF was refluxed for 2 hours and then stirred overnight at room temperature. After cooling to room temperature, the mixture was evaporated and the residue was suspended in 15 mL of hot water. After cooling to room temperature, the final precipitate was isolated via filtration, washed with water, dissolved in acetonitrile and dried in vacuo to yield 159 mg of 6-hydrazinopyrimidine-4-carbonitrile hydrochloride. The mother liquor obtained from the filtration step was then basified using an aqueous solution of NaHCO ₃ . This results in incomplete dissolution of some solid precipitates formed after filtration. The complete suspension was transferred to a separatory funnel and extracted three times with ethyl acetate. The combined organic layer was washed with brine, dried over Na ₂ SO ₄ and filtered. Evaporation of the solvent under reduced pressure gave 120 mg of 6-hydrazinopyrimidine-4-carbonitrile. The obtained 6-hydrazinopyrimidine-4-carbonitrile hydrochloride and 6-hydrazinopyrimidine-4-carbonitrile were combined and used in the next step without further purification.

ESI mass [m/z]: 136.1 [M+H] ⁺

Step 2: tert-butyl {1-[1-(6-cyanopyrimidin-4-yl)-1H-1,2,4-triazol-5-yl]ethyl}carbamate

To a solution of 0.26 g (1.35 mmol) N ² -(tert-butoxycarbonyl)-alaninamide in 10 mL CH ₂ Cl ₂ was added 0.27 mL (2.0 mmol) N,N-dimethylformamide dimethylacetal. The solution was heated at reflux for 2 h after which time the solvent was removed under reduced pressure. The residue was dissolved in a mixture of 3 mL glacial acetic acid and 3 mL 1,4-dioxane. A mixture of 0.27 g of 6-hydrazinopyrimidine-4-carbonitrile and 6-hydrazinopyrimidine-4-carbonitrile hydrochloride obtained in the first step was mixed with 2 mL glacial acetic acid and 2 mL 1,4-dioxane. Added as a solution in the mixture. The mixture was stirred at room temperature for 72 hours. Then the solvent was removed under reduced pressure and the residue was purified via chromatography on silica (ethyl acetate/cyclohexane) to yield 201 mg of tert-butyl {1-[1-(6-cyanopyrimidin-4-yl) -1H-1,2,4-triazol-5-yl]ethyl}carbamate was provided.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ = 9.38 (s, 1H), 8.58 (s, 1H), 8.33 (s, 1H), 7.61 (d, J = 7.6 Hz, 1H), 5.78 - 5.68 (m, 1H), 1.44 (d, J = 7.6 Hz, 3H), 1.33 (s, 9H).

ESI mass [m/z]: 316.1 [M+H] ⁺

Step 3: 6-[5-(1-aminoethyl)-1H-1,2,4-triazol-1-yl]pyrimidine-4-carbonitrile hydrochloride

100 mg (0.31 mmol) tert-butyl {1-[1-(6-cyanopyrimidin-4-yl)-1H-1,2,4-triazole-5- in 3 mL 1,4-dioxane To a solution of yl]ethyl}carbamate was added 0.79 mL (3.2 mmol) of a 4 M solution of HCl in 1,4-dioxane, and the mixture was stirred at room temperature overnight. Next, an additional 0.50 mL (2.0 mmol) of a 4 M solution of HCl in 1,4-dioxane was added and the mixture was stirred at room temperature overnight. Evaporation of the reaction mixture gave the title compound (100 mg, 80% purity) which was used in the next step without further purification.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ = 9.42 (d, J = 1.2 Hz, 1H), 8.74 (brs, 3H), 8.67 (d, J = 1.2 Hz, 1H), 8.56 (s , 1H), 5.50 - 5.40 (m, 1H), 1.64 (d, J = 6.8 Hz, 3H).

ESI mass [m/z]: 216.1 [amine+H] ⁺

Step 4: N-{1-[1-(6-cyanopyrimidin-4-yl)-1H-1,2,4-triazol-5-yl]ethyl}-3-cyclopropyl-5-(trifluoro -methoxy)benzamide (Example I-8)

To a solution of 67 mg (64% purity, 0.18 mmol) 3-cyclopropyl-5-(trifluoromethoxy)benzoic acid in 2 mL N,N -dimethylformamide (DMF) was added 0.1 mL (0.6 mmol) N,N - Diisopropylethylamine (Hunig's base) and 121 mg (318 μmol) [ O- (7-azabenzotriazol-1-yl) -N,N,N',N'- tetramethyluronium-hexafluoro rophosphate] (HATU) was added. The mixture was stirred at room temperature for 1 hour. Next, 50 mg (80% purity, 0.15 mmol) 6-[5-(1-aminoethyl)-1H-1,2,4-triazol-1-yl]pyrimidine-4-carbonitrile hydrochloride was added and the reaction mixture was stirred at room temperature for 3 days. The reaction mixture was then purified directly via reverse phase chromatography (water/acetonitrile) to give 31 mg of the title compound.

ESI mass [m/z]: 444.1 [M+H] ⁺

1H ^- NMR (400 MHz, DMSO-d ₆ ): δ = 9.38 (d, J = 0.8 Hz, 1H), 9.24 (d, J = 6.8 Hz, 1H), 8.61 (d, J = 0.8 Hz, 1H) ), 8.35 (s, 1H), 7.54 (s, 1H), 7.52 (s, 1H), 7.28 (s, 1H), 6.22-6.12 (m, 1H), 2.10 - 2.00 (m, 1H), 1.63 d, J = 7.2 Hz, 3H), 1.07 - 1.00 (m, 2H), 0.81 - 0.75 (m, 2H).

Synthesis of methyl 3-bromo-5- (difluoromethoxy) benzoate

Step 1: Methyl 3-bromo-5-hydroxybenzoate

A solution of 3-bromo-5-hydroxybenzoic acid (49.9 g, 230 mmol) in MeOH (325 mL) was cooled via an ice bath to 7-8 °C. Next, SOCl ₂ (27.4 g, 16.79 mL, 230 mmol) was added drop wise to this solution over 25 minutes. The reaction mixture was warmed to room temperature, stirred at reflux for 3 hours, cooled to room temperature and then stirred at this temperature for an additional 48 hours. All volatiles were removed in vacuo and the residue was dissolved in ethyl acetate (400 mL). The solution was washed with NaHCO ₃ , brine, dried over Na ₂ SO ₄ then the volatiles were removed under reduced pressure. The residue was triturated with hexanes (400 mL). The precipitate was filtered, washed with hexane/diethyl ether (1:1), and dried at 110° C. to give methyl 3-bromo-5-hydroxybenzoate (50.5 g) as a dark yellow powder.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 7.73 (m, 1H), 7.51 (m, 1H), 7.26 (s, 1H), 7.23 (t, J = 2.1 Hz, 1H), 6.05 (br s, 1H), 3.92 (s, 3H). Recorded on a Varian Gemini 2000 machine.

Step 2: Methyl 3-bromo-5-(difluoromethoxy)benzoate

A mixture of methyl 3-bromo-5-hydroxybenzoate (23.1 g, 100 mmol), K ₂ CO ₃ (41.5 g, 300 mmol) and ClF ₂ CCOONa (45.7 g, 300 mmol) in DMF (350 mL) was stirred at 60-65 °C for 2 hours. The precipitate was then separated, washed with acetone and the filtrate evaporated under reduced pressure. The residue was dissolved in diethyl ether (300 mL) and the solution was allowed to stand at room temperature for 12 hours. A precipitate formed which was filtered and washed with water. The filtrate was washed with brine (300 mL) and the organic layer was evaporated under reduced pressure. The oily residue was dissolved in hexanes (250 mL) and kept at room temperature for 2 hours. The precipitate formed was removed by filtration and the filtrate was evaporated under reduced pressure. The residue was distilled under reduced pressure (3 torr) and fractions with a boiling point between 80 and 85° C. were collected to give 15.75 g methyl 3-bromo-5-(difluoromethoxy)benzoate.

1H NMR (400 MHz, CDCl ³ ) δ = 8.03 ₍ t, J = 1.6 Hz, 1H), 7.75 - 7.70 (m, 1H), 7.49 (t, J = 2.1 Hz, 1H), 6.55 (t, J = 72.6 Hz, 1H), 3.93 (s, 3H). Recorded on a Varian Gemini 2000 machine.

¹⁹ F NMR (376 MHz, CDCl ₃ ) δ = -84.89 (d, J = 72.7 Hz). (recorded from a Varian Gemini 2000 machine)

Synthesis of 3-methylsulfonyl-5-(trifluoromethoxy)benzoic acid

A mixture of 2.95 g (17.5 mmol) trans- N,N -dimethylcyclohexane-1-2-diamine and 11.4 g (35 mmol) cesium carbonate in 60 mL DMF was degassed for 30 minutes by purging with argon. 5 g (17.5 mmol) 3-bromo-5-(trifluoromethoxy)benzoic acid, 3.58 g (35 mmol) sodium methanesulfinate and 3.34 g (17.5 mmol) copper(I) iodide were added and the mixture was further purged with argon for 5 minutes. The mixture was stirred at 120° C. overnight, cooled to room temperature and then extracted three times with dichloromethane. The aqueous layer was acidified with concentrated hydrochloric acid to pH 2 and extracted again with dichloromethane. The dichloromethane layer was washed several times with brine. The layers were separated and the combined organic layers were dried over anhydrous Na ₂ SO ₄ and filtered. The solvent was removed under reduced pressure and the residue was triturated with n-pentane, filtered and dried to give 3.2 g of 3-methylsulfonyl-5-(trifluoromethoxy)benzoic acid.

¹ H NMR (DMSO-d ₆ , 400 MHz): δ = 14.00 (br s, 1H, COOH), 8.42 (s, 1H), 8.20 (s, 1H), 8.14 (s, 1H), 3.39 (s, 3H).

ESI mass [m/z]: 285.0 [M+H] ⁺

In a similar manner, the following intermediates were prepared:

3-(Cyclopropylsulfonyl)-5-(trifluoromethoxy)benzoic acid

ESI mass [m/z]: 311.0 [M+H] ⁺

3-Chloro-5-(4-chlorophenyl)sulfonyl-benzoic acid

ESI mass [m/z]: 331.0 [M+H] ⁺

Synthesis of 3-(difluoromethoxy)-5-methylsulfonyl-benzoic acid

Step 1: Methyl 3-(trifluoromethoxy)-5-triisopropylsilylsulfanyl-benzoate

To a stirred solution of triisopropylsilanethiol (21.45 g, 112 mmol) in toluene (500 mL), under a stream of argon, was added NaH (5.03 g, 122 mmol, 60% disperse in oil) in portions. The mixture was stirred until no more gas was evolved. Next, methyl 3-bromo-5-(trifluoromethoxy)benzoate (CAS: 1306763-53-0) (30 g, 100 mmol), xantphos (6.13 g, 11.2 mmol) and Pd ₂ (dba ) ₃ (4.85 g, 5.3 mmol) were added sequentially to the reaction mixture. The mixture was stirred at 100 °C overnight, then cooled to room temperature, diluted with EtOAc (500 mL) and filtered through a thin film of silica gel. After evaporation, crude methyl 3-(trifluoromethoxy)-5-triisopropylsilylsulfanyl-benzoate (50 g, 50% pure by LC/MS, 64 mmol, 57% yield) was obtained by adding It was used in the next step without purification.

Step 2: Methyl 3-(difluoromethylsulfanyl)-5-(trifluoromethoxy)benzoate

To a stirred solution of crude methyl 3-(trifluoromethoxy)-5-triisopropylsilylsulfanyl-benzoate (50 g, 50% pure by LC/MS, 64 mmol) in DMF (1000 mL) was added sodium 2-Chloro-2,2-difluoroacetate (29.27 g, 192 mmol) and cesium carbonate (62.55 g, 192 mmol) were added under a stream of argon. The mixture was stirred at 100 °C overnight, cooled to room temperature and evaporated under reduced pressure. The residue was dissolved in water (1000 mL) and extracted with EtOAc (5 Х 250 mL). Methyl 3-(difluoromethylsulfanyl)-5-(trifluoromethoxy)benzoate (10.5 g, 34.7 mmol, 54.3% yield) was obtained after column chromatography.

Step 3: Methyl 3-(difluoromethylsulfonyl)-5-(trifluoromethoxy)benzoate

To a solution of methyl 3-(difluoromethylsulfanyl)-5-(trifluoromethoxy)benzoate (10.5 g, 34.7 mmol) in dichloromethane (200 mL) was added mCPBA (16.35 g, 93.9 mmol, 75% purity). ) was added in portions at 0° C. under a stream of argon. The mixture was stirred overnight at room temperature and evaporated under reduced pressure. Methyl 3-(difluoromethylsulfonyl)-5-(trifluoromethoxy)benzoate (6.8 g, 20.34 mmol, 58.63%) was obtained after column chromatography on silica gel.

Step 4: 3-(difluoromethylsulfonyl)-5-(trifluoromethoxy)benzoic acid

LiOH to a stirred solution of methyl 3-(difluoromethylsulfonyl)-5-(trifluoromethoxy)benzoate (6.8 g, 20.34 mmol) in THF (80 mL)/water (20 mL) mixture at 0 °C. Monohydrate (1.146 g, 27.459 mmol) was added and the mixture was stirred overnight at room temperature. THF was evaporated under reduced pressure, the aqueous layer was acidified to pH=3 and extracted with MTBE (5 Х 10 mL). Pure 3-(difluoromethylsulfonyl)-5-(trifluoromethoxy)benzoic acid (3 g, 9.37 mmol, 34.12% yield) was obtained as a white solid after recrystallization from 30% aqueous EtOH.

¹ H NMR (DMSO-d ₆ , 400 MHz): δ = 7.47 (t, 1H), 8.21 (s, 1H), 8.32 (s, 1H), 8.40 (s, 1H), 13.79 (s, 1H).

ESI mass [m/z]: 319.0 [M+H] ⁺

2-Chloro-6-(1-cyanocyclopropyl)-N-[(1S)-1-[2-(6- cyanopyrimidin-4- yl)-1,2,4-triazole-3 Synthesis of -yl]ethyl]pyridine-4-carboxamide (I-35)

Step 1 : 2-Chloro-6-(cyanomethyl)pyridine-4-carboxylic acid

n- BuLi (91.14 mL, 2M, 183.3 mmol)) was diluted in anhydrous THF (150 mL) and cooled under argon to -78 °C. A solution of anhydrous acetonitrile (11.4 ml, 218.8 mmol) in anhydrous THF (30 mL) was added dropwise and the reaction mixture was kept at -78°C for 30 min. A solution of 2,6-dichloropyridine-4-carboxylic acid (7 g, 36.5 mmol) in THF (200 mL) was added dropwise over 1 hour and the reaction mixture was stirred at -78 °C for another 45 minutes, then 1 hour. while stirring at room temperature. The reaction mixture was then quenched with saturated aqueous citric acid solution (200 mL) and extracted with EtOAc (3 x 250 mL). The organic layer was washed with water (3 x 300 mL) then brine solution (200 mL) and dried over anhydrous Na ₂ SO ₄ and the solvent was removed under reduced pressure. The residue was purified via flash silica gel chromatography using a gradient of 0% to 10% acetone in DCM. The obtained solid was triturated with 50% diethyl ether in n -pentane to give 4.2 g (58% yield) of 2-chloro-6-(cyanomethyl)pyridine-4-carboxylic acid as an off-white solid.

¹ H NMR (400 MHz, D6-DMSO): δ = 7.87 (s, 1H), 7.82 (s, 1H), 4.27 (s, 2H). COOH not detected.

ESI mass [m/z]: 195.0 [MH] ^-

Step 2: 2-Chloro-6-(1-cyanocyclopropyl)pyridine-4-carboxylic acid (INT-12)

To a stirred solution of 2-chloro-6-(cyanomethyl)pyridine-4-carboxylic acid (3.5 g, 17.8 mmol) in acetonitrile (50 mL) under nitrogen was added tetrabutylammonium bromide (5.74 g, 17.8 mmol). added. Next, 1,2-dibromoethane (3.68 g, 19.6 mmol) was added dropwise at room temperature, then the reaction mixture was stirred at room temperature for an additional 30 minutes. The reaction mixture was cooled to 0 °C. 7.5 mL of aqueous NaOH solution (50%) was slowly added dropwise over 20 minutes. The reaction mixture was then allowed to warm to room temperature and stirred for an additional 24 hours. The reaction mixture was concentrated under vacuum at room temperature. The remaining residue was diluted with water, acidified with citric acid (pH∼5) and extracted with EtOAc (3 x 150 mL). The combined organic layers were washed with water (3 x 100 mL) and sodium thiosulfate solution (100 mL) followed by brine solution (150 mL). The organic layer was dried over anhydrous Na ₂ SO ₄ then the solvent was removed under reduced pressure. The crude material was purified via flash silica gel chromatography using a gradient of 0% to 10% acetone in DCM. The final solid was washed with n -pentane to give 2 g (50% yield) of 2-chloro-6-(1-cyanocyclopropyl)pyridine-4-carboxylic acid (INT-12) as an off-white solid.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ = 14.20 (bs, 1H, COOH), 7.89 (s, 1H), 7.53 (s, 1H), 1.94 - 1.91 m, 2H), 1.76 - 1.73 ( m, 2H).

ESI mass [m/z]: 221.0 [MH] ^-

Step 3: tert-Butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo - ethyl]carbamate

tert-Butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (40.0 g, 213 mmol) was dissolved in DCM (400 mL). Dimethylformamide dimethylacetal (38.0 g, 319 mmol, 42.4 mL) was added to the mixture. The reaction mixture was stirred at 40 °C for 2 hours. The reaction mixture was concentrated under reduced pressure. tert-Butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]carbamate (50.0 g, crude) was obtained as a colorless oil, crude material was used in the next step.

Step 4: tert-butyl N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (INT-3)

tert-Butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]carbamate (36.1 g, 267 mmol) in dioxane (400 mL) dissolved 6-hydrazinopyrimidine-4-carbonitrile (50.0 g, 206 mmol) was dissolved in AcOH (400 mL) and added to the mixture. The reaction mixture was stirred at 20 °C for 16 hours. The reaction mixture was concentrated under reduced pressure. The residue was purified via column chromatography (SiO ₂ , petroleum ether/EtOAc = 50/1 to 0/1). The crude product was triturated with MTBE (750 mL) at 20 °C for 30 min. tert-butyl-N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (INT-3 ) (8.50 g, 27.0 mmol, 13.1% yield) was obtained as a white solid.

The enantiomeric excess of INT-3 was determined via the screen OD_RH (acid): ee-value = 95%; R _t = 9.49 min. Method: Chiral HPLC; Chiralcel OD-RH column (4.6 mm x 150 mm x 5 μm), room temperature, eluting with 0.1% phosphoric acid (A) and acetonitrile (B), gradient A:B 95/5 to 10/90, λ = 210 nm detected in.

1H NMR (400 MHz, CDCl3): δ ⁼ 1.43 (s, 9H), 1.58 (d, J = 6.8 Hz, 3H), 5.45 - 5.58 (m, 1H), 5.97 - 6.10 (m, 1H), 8.02 (s, 1H), 8.32 (d, J = 0.8 Hz, 1H), 9.24 (d, J = 1.2 Hz, 1H). Measured on Bruker AVANCE III 400 MHz.

ESI mass [m/z]: 260.1 [MC ₄ H ₈ +H] ⁺

Step 5: 6-[5-[(1S)-1-aminoethyl]-1,2,4-triazol-1-yl]pyrimidine-4-carbonitrile; 2,2,2-trifluoroacetic acid (INT-4)

tert-butyl-N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (2 g, 6.34 mmol) was dissolved in 20 mL dichloromethane. Trifluoroacetic acid (3.62 g, 31.7 mmol) was added slowly, then the reaction mixture was stirred at room temperature overnight and then heated to 40° C. for 3 hours to complete the reaction. The reaction mixture was evaporated under reduced pressure and used as crude in the next step.

ESI mass [m/z]: 216.1 [amine+H] ⁺

Step 5: 2-Chloro-6-(1-cyanocyclopropyl)-N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-1,2,4-triazole-3 -yl] ethyl] pyridine-4-carboxamide (I-35)

2-Chloro-6-(1-cyanocyclopropyl)pyridine-4-carboxylic acid (88 mg, 0.39 mmol) was dissolved in 10 mL dichloromethane, followed by 2 drops of DMF followed by oxalyl chloride (114 mg, 0.9 mmol) was added. The reaction mixture was stirred until gas evolution ceased. The reaction mixture was then evaporated under reduced pressure and dissolved in acetonitrile. This solution was diluted with 6-[5-[(1S)-1-aminoethyl]-1,2,4-triazol-1-yl]pyrimidine-4-carbonitrile (2,2,2-trifluoro Rhoacetic acid salt) (197 mg 60% pure, 0.36 mmol) and DIPEA (140 mg, 1.08 mmol) was slowly added dropwise to another acetonitrile solution. The reaction mixture was stirred overnight at room temperature, then diluted with water and dichloromethane, and the organic layer was separated and evaporated under reduced pressure. The remaining residue was purified via HPLC means to give the title compound as an off-white solid (86 mg, 56 % yield).

¹ H NMR see the peak list in Table 1.

ESI mass [m/z]: 420.3 [M+H] ⁺

3-Bromo-N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl] -5-(trifluoromethoxy)benzamide (I-15) and 6-[5-[(1S)-1-[[3-bromo-5-(trifluoromethoxy)benzoyl] amino] ethyl] Synthesis of -3-cyclopropyl-1,2,4-triazol-1-yl] pyrimidine-4-carboxamide (I-13)

Step 1 : Ethyl cyclopropanecarboxymidate hydrochloride

Cyclopropanecarbonitrile (10.0 g, 149 mmol, 11.0 mL) was dissolved in HCl/dioxane (70.0 mL). EtOH (6.87 g, 149 mmol, 8.71 mL) was added dropwise slowly at 0 °C. The mixture was stirred at 25° C. for 16 hours. The reaction mixture was concentrated under reduced pressure to remove HCl/dioxane. The crude product was milled with MTBE at 25° C. for 30 min and then filtered. The filter cake was dried under reduced pressure using a rotary evaporator. The crude product (21.0 g, 140 mmol, 94.2% yield, HCl salt) was obtained as a white solid and used in the next step without further purification.

Step 2 : Ethyl (Z)-N-[(2S)-2-(tert-butoxycarbonylamino)propanoyl]cyclopropanecarboxymidate

tert-Butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (15.1 g, 79.7 mmol) was dissolved in THF (180 mL). Ethyl cyclopropanecarboxymidate hydrochloride (17.8 g, 119 mmol), DIPEA (46.1 g, 357 mmol, 62.1 mL) and finally HATU (49.7 g, 131 mmol) were added. The mixture was stirred at 25 °C for 3 hours. Ethyl (Z)-N-[(2S)-2-(tert-butoxycarbonylamino)propanoyl]cyclopropanecarboxymidate (22.5 g, crude) in THF was obtained as a yellow liquid which was obtained in the next step It was used as a solution without further workup and purification.

Step 3 : tert-Butyl N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl ]Carbamate (INT-7)

6-hydrazinopyrimidine- 4-carbonitrile (7.13 g, 52.8 mmol) was added slowly at 0 °C. The mixture was stirred at 25° C. for 16 hours. The reaction mixture was quenched with H ₂ O (200 mL) then extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with brine (200 mL), dried over anhydrous Na ₂ SO ₄ , filtered and concentrated in vacuo. The obtained residue was purified via column chromatography (SiO2, petroleum ether/ethyl acetate = 50/1 to 3/1) to give tert-butyl N-[(1S)-1-[2-(6-cyanopyryl Midin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]carbamate (INT-7, 5.60 g, 15.6 mmol, 29.6% yield, 99.1% purity) was obtained as white Provided as a solid.

The enantiomeric excess of INT-7 was determined via the screen OD_RH (acid): ee-value = 92.5%; R _t = 14.45 min. Method: Chiral HPLC; Chiralcel OD-RH column (4.6 mm x 150 mm x 5 μm), room temperature, eluting with 0.1% phosphoric acid (A) and acetonitrile (B), gradient A:B 95/5 to 10/90, λ = 210 nm detected in.

1H NMR (400 MHz, ^MeOD ): δ = 9.21 (s, 1H), 8.36 (s, 1H), 5.82 (q, J=6.8 Hz, 1H), 2.15 - 2.04 (m, 1H), 1.52 (d , J=6.8 Hz, 3H), 1.40 (br s, 9H), 1.09 - 0.98 (m, 4H). Measured with Bruker AVANCE III 400 MHz.

ESI mass [m/z]: 356.0 [M+H] ⁺

Step 4 : 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carbonitrile hydrochloride (INT-8 ) and 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride (INT-11 )

tert-Butyl N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]carbamate (5.0 g, 14 mmol) was dissolved in 4M HCl/dioxane (35.0 mL) and stirred overnight at room temperature. HCl/dioxane was removed under reduced pressure. The remaining solid is 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carbonitrile hydrochloride (INT-8 ) and 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride (INT-11 ) and was used in the next step without further purification.

6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carbonitrile hydrochloride (INT-8)

ESI mass [m/z]: 256.2 [amine+H] ⁺

6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride (INT-11)

ESI mass [m/z]: 274.2 [amine+H] ⁺

Step 5 : 3-Bromo-N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl ]ethyl]-5-(trifluoromethoxy)benzamide (I-15) and 6-[5-[(1S)-1-[[3-bromo-5-(trifluoromethoxy) benzoyl]amino ]ethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide (I-13)

101 mg (0.28 mmol) 3-bromo-5-(trifluoromethoxy)benzoic acid, 245 mg (0.65 mmol) 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4 A mixture of ,5-b]pyridium 3-oxide hexafluorophosphate (HATU), 146 mg (1.13 mmol) N,N -diisopropylethylamine and 1.3 mL DMF was stirred at room temperature for 60 minutes. 100 mg of the mixture from step 4 was added and the reaction mixture was stirred overnight at room temperature. The mixture was diluted with water and extracted with DCM, the DCM layer was separated, washed with brine, then concentrated under reduced pressure and purified via preparative HPLC chromatography to give 11 mg (6.5% yield) of 3-bromo- N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]-5-(tri Fluoromethoxy)benzamide (I-15) and 94.5 mg (54.2% yield) of 6-[5-[(1S)-1-[[3-bromo-5-(trifluoromethoxy)benzoyl]amino ]ethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide (I-13).

3-Bromo-N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl] -5-(trifluoro-methoxy)benzamide (I-15)

¹ H NMR see the peak list in Table 1.

ESI mass [m/z]: 524.1 [M+H] ⁺

6-[5-[(1S)-1-[[3-Bromo-5-(trifluoromethoxy)benzoyl]amino]ethyl]-3-cyclopropyl-1,2,4-triazole-1- yl]pyrimidine-4-carboxamide (I-13)

¹ H NMR see the peak list in Table 1.

ESI mass [m/z]: 542.1 [M+H] ⁺

Synthesis of intermediate 6-hydrazinopyrimidine-4-carboxamide / (6-hydrazono-1,6-dihydropyrimidine-4-carboxamide)

Step 1: 6-chloropyrimidine-4-carbonyl chloride

Oxalyl chloride (26.0 mL, 297.0 mmol) was prepared by heating of 6-hydroxypyrimidine-4-carboxylic acid (13.86 g, 9.98 mmol) and DMF (0.13 mmol, 0.01 mL) in 80 mL ethyl acetate for 1 hour. added to the mixture. Heating under reflux was continued for 3 hours. The volatiles were distilled off under ambient pressure followed by reduced pressure. Kugelrohr distillation (diaphragm pump vacuum, 6 mbar, oven temp 110° C.) yielded 11.03 g (63% of theory).

Step 2: 6-chloropyrimidine-4-carboxamide

6-Chloropyrimidine-4-carbonyl chloride (11.03 g, 62.32 mmol) in THF (50 mL) was cooled in ice/water within 10 min in a mixture of THF/cold water (0.3 L) aq. After addition of ammonia (33%, 20 ml, 341 mmol), the mixture was stirred for 1 hour. The mixture was aq. It was acidified with HCl and the organic solvent was removed under reduced pressure. The precipitate formed was filtered, washed with water and dried to yield 7.6 g (76% of theory, corrected for purity).

ESI mass [m/z]: 158.1 [M+H] ⁺

¹ H NMR (400 MHz, D ₆ -DMSO): δ = 8.1 (m, 2H), 8.45 (br, 1H), 9.2 (s, 1H).

Step 3: 6-hydrazinopyrimidine-4-carboxamide/(6-hydrazono-1,6-dihydropyrimidine-4-carboxamide)

6-Chloropyrimidine-4-carboxamide (7.06 g, 48.24 mmol) and hydrazine hydrate (64%, 10.32 g, 206.1 mmol, 10.0 mL) in MeOH (250 mL) were stirred at 65 °C for 4 hours. Water was added and MeOH was evaporated under reduced pressure. Aq. HCl and aq. K ₂ CO ₃ was added until pH 8. The precipitate formed was filtered, washed with water and dried to yield 7.03 g (95% of theory, corrected for purity).

ESI mass [m/z]: 154.1 [M+H] ⁺

¹ H NMR (400 MHz, D ₆ -DMSO): δ = 4.5 (br, 2H), 7.3 (br, 1H), 7.7 (br, 1H), 8.0 (br, 1H), 8.4 (br, 1H), 8.7 (br, 1H).

6-[5-[(1S)-1-[(3,5-dibromobenzoyl)amino]ethyl]-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide ( Synthesis of I-34)

Step 1: 3,5-Dibromo-N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo - ethyl]benzamide

0.5 g (1.4 mmol) N-[(2S)-1-amino-1-oxopropan-2-yl]-3,5-dibromobenzamide in 40 mL THF and 3 mL DMF-DMA (22,6 mmol) was stirred in a water bath of a rotary evaporator at a water bath temperature of 65° C. for 10 minutes and then evaporated under reduced pressure to give 0.61 g, which was used directly in the next step.

Step 2: 6-[5-[(1S)-1-[(3,5-dibromobenzoyl)amino]ethyl]-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide ( I-34)

0.61 g (1.5 mmol) 3,5-dibromo-N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]benzamide and 0.25 g ( 1.6 mmol) 6-hydrazinopyrimidine-4-carboxamide was stirred in 60 mL AcOH at 85° C. for 0.5 h. The mixture was evaporated under reduced pressure and aq. K ₂ CO ₃ , aq. NaCl and EtOAc were added. The aqueous layer was extracted 3 times with THF/EtOAc. The combined organic layers were dried over Na ₂ SO ₄ and evaporated under reduced pressure. Crystallization of the residue from MeOH (including heating with activated carbon and hot filtration) yielded 0.24 g (32%).

See Table 1 for analytical data.

Synthesis of 6-[5-[(1S)-1-aminoethyl]-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride (INT-9)

Step 1: tert-Butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl- 2-oxo- ethyl]carbamate

tert-Butyl N-[(1S)-2-amino-1-methyl-2-oxo-ethyl]carbamate (150 g, 797 mmol, 1.00 eq) was dissolved in dioxane (1.50 L). N,N -Dimethylformamide dimethylacetal (142 g, 1.20 mol, 159 mL, 1.50 eq) was added to the mixture. The reaction mixture was stirred at 25 °C for 3 hours. TLC (dichloromethane: methanol = 10:1, Rf = 0.67) indicated that the starting material was consumed. The crude product (193 g, calc.) in dioxane was used in the next step without further purification.

Step 2: tert-Butyl N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate

The reaction mixture of tert-butyl N-[(1S)-2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]carbamate (193 g, 793 mmol, 1.00 eq) was AcOH (6-chloropyrimidin-4-yl)hydrazine (126 g, 873 mmol, 1.10 eq) dissolved in (1900 mL). The reaction mixture was stirred at 25 °C for 16 hours. TLC (petroleum ether: ethyl acetate = 3:1, Rf = 0.22) indicated complete consumption of the starting material. The reaction mixture was concentrated under vacuum. The residue was purified via column chromatography (silica gel, petroleum ether/ethyl acetate = 50/1 to 3/1). tert-butyl N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (160 g, 493 mmol , 62.1% yield) as a white solid.

Step 3: Methyl 6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1-yl]pyrimidine-4-carboxylate

tert-Butyl N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate in MeOH (1.50 L) (80.0 g, 246 mmol, 1.00 eq) was added to triethylamine (49.9 g, 493 mmol, 68.6 mL, 2.00 eq) and Pd(dppf)Cl ₂ (18.0 g, 24.6 mmol, 0.100 eq) under nitrogen. did The suspension was degassed under vacuum and purged several times with CO (carbon monoxide). The mixture was stirred at 40° C. under CO (246 mmol, 1.00 eq) (50.0 psi) for 16 h. TLC (petroleum ether: ethyl acetate = 1:1, Rf = 0.27) indicated that the starting material was consumed. The reaction mixture was filtered and the filtrate was concentrated under vacuum. The residue was purified via column chromatography (silica gel, petroleum ether/ethyl acetate = 50/1 to 1/1). Methyl 6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1-yl]pyrimidine-4-carboxylate (80.0 g, 230 mmol, 46.6% yield) as a white solid.

¹ H NMR (DMSO-d ₆ ) δ = 9.29 (s, 1H), 8.63 (s, 1H), 8.02 (s, 1H), 7.27 (s, 1H), 6.09 - 6.06 (m. 1H), 5.58 - 5.56 (d, 1H), 1.60 - 1.58 (d, 3H), 1.42 (s, 9H).

Step 4: tert-Butyl N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate

Methyl 6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-1,2,4-triazol-1-yl]pyrimidine-4-carboxylate (40.0 g, 115 mmol, 1.00 eq) was dissolved in THF (240 mL) and MeOH (80.0 mL). NH ₄ OH (96.6 g, 689 mmol, 106 mL, 25.0% purity, 6.00 eq) was added to the mixture. The reaction mixture was stirred at 25° C. for 6 hours. TLC (petroleum ether: ethyl acetate = 3:1, Rf = 0.1) indicated complete consumption of the starting material. The reaction mixture was concentrated. The crude product was triturated with MTBE (300 mL) at 25 °C for 30 min. tert-butyl N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (64.0 g, 189 mmol, 82.1% yield, 98.2% purity) was obtained as a white solid.

¹ H NMR (DMSO-d ₆ ) δ = 9.30 (s, 1H), 8.47 (s, 1H), 8.35 (s, 1H), 8.28 (s, 1H), 8.12 (s, 1H), 5.80 - 5.76 ( m. 1H), 1.46 - 1.44 (d, 3H), 1.32 (s, 9H).

Step 5: 6-[5-[(1S)-1-aminoethyl]-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride (INT-9)

tert-butyl N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate (1 g, 3 mmol) in 30 mL dioxane, then 4 M HCl/dioxane (7.5 mL) was added and the mixture was stirred at 50° C. for 7 h and further for 4 days at room temperature. The mixture was evaporated under reduced pressure to give 1.02 g of crude product (INT-9).

ESI mass [m/z]: 234.2 [amine+H] ⁺

¹ H NMR (DMSO-d ₆ ) δ = 9.36 (s, 1H), 8.78 (s, 2H, NH ₂ ), 8.52 (s, 1H), 8.50 (bs, 1H), 8.39 (s, 1H), 8.17 (bs, 1H), 5.07 - 5.45 (m, 1H), 1.67 - 1.65 (d, 3H).

Synthesis of 3-(trifluoromethoxy)-5-(trifluoromethylsulfonyl)benzoic acid (INT-13)

Step 1: 3-Bromo-5-(trifluoromethoxy)benzenethiol

A 2.5 M solution of n-BuLi in hexane (77 mL, 191 mmol) was dissolved in 1,3-dibromo-5-(trifluoromethoxy)benzene (48.9 g) in anhydrous diethyl ether (430 mL) at -65 °C. , 153 mmol) of the stirred solution. The reaction mixture was stirred at -65 °C for 50 min. Then ground sulfur (7.11 g, 222 mmol) was added portionwise at -65 °C. The reaction mixture was stirred at -65 °C for 1.5 h. Next, glacial acetic acid (35 mL) was added to the stirred reaction mixture. The mixture was allowed to reach 0 °C. The reaction mixture was concentrated under reduced pressure to a volume of 50 mL. The residue was triturated with deionized water (500 mL) and the final emulsion was extracted with diethyl ether (2Х300 mL). The combined diethyl ether layers were successively washed with water and brine and the solution was dried over sodium sulfate. The solvent was removed under reduced pressure to give a brown oil. The oil was vacuum distilled at a pressure of 13 mm Hg. A colorless fraction was obtained at 94-98°C. Yield 27.7 g (66%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.35 (t, J = 1.6 Hz, 1H), 7.19 - 7.16 (m, 1H), 7.08 - 7.05 (m, 1H), 3.61 (s, 1H) . ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ = -57.80. ¹ H and ¹⁹ F NMR spectra recorded on a Varian Gemini 2000 instrument.

Step 2: 1-Bromo-3-(trifluoromethoxy)-5-(trifluoromethylsulfanyl)benzene

Triethylamine (27.2 mL, 195 mmol) was added to a degassed solution of 3-bromo-5-(trifluoromethoxy)benzenethiol (17.75 g, 65 mmol) in DMF (175 mL) under argon. The stirred mixture was cooled to 0° C. and blown with trifluoroiodomethane until a weight gain of 38 g. 1,1'-Dimethyl-[4,4'-bipyridine]-1,1'-dium dichloride (3.34 g, 13 mmol) was then added to the stirred reaction mixture. The reaction mixture was stirred overnight at room temperature. The mixture was poured into deionized water (800 mL) and the final emulsion was extracted with diethyl ether (2Х350 mL). The combined diethyl ether layers were washed successively with water and brine, and the solution was dried over sodium sulfate. The solvent was removed under reduced pressure to give a dark brown oil. The oil was vacuum distilled at a pressure of l20 mm Hg. A colorless fraction was obtained at 87-89°C. Yield 23.4 g (83%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.76 (t, J = 1.6 Hz, 1H), 7.54 - 7.51 (m, 1H), 7.49 - 7.47 (m, 1H). ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ = -41.92, -58.01. ¹ H and ¹⁹ F NMR spectra recorded on a Varian Gemini 2000 instrument.

Step 3: 3-(trifluoromethoxy)-5-(trifluoromethylsulfanyl)benzoic acid

1-bromo-3-(trifluoromethoxy)-5-(trifluoromethylsulfanyl)benzene (5.12 g, 15 mmol), ground potassium carbonate (10.4, 75 mmol), palladium in DMF (75 mL) (II) A stirred mixture of acetate (168 mg, 0.75 mmol), and xantphos (868 mg, 1.5 mmol) was heated at 100° C. under a carbon monoxide atmosphere for 19 hours. Deionized water (75 mL) was added to the reaction mixture at room temperature. Solvent was removed under reduced pressure. The residue was dissolved in deionized water (70 mL) and extracted with diethyl ether (2Х50 mL). The aqueous layer was separated and its pH was adjusted to 4 with aqueous HCl. The solvent was removed under reduced pressure and the residue was purified via column chromatography on silica gel (Combiflash). Yield 3 g (65%).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ = 13.94 (s, 1H), 8.19 (t, J = 1.5 Hz, 1H), 8.07 - 8.04 (m, 1H), 8.03 - 8.00 (m, 1H). ¹⁹ F-NMR (376 MHz, DMSO-d ₆ ): δ = -44.12, -59.52. ¹ H and ¹⁹ F NMR spectra recorded on a Varian Gemini 2000 instrument.

Step 4: 3-(trifluoromethoxy)-5-(trifluoromethylsulfonyl)benzoic acid (INT-13)

An aqueous solution of hydrogen peroxide (40%, 20 mL, 100 mmol) was added drop wise to a stirred solution of TFA (0.3 mL) in acetic anhydride (50 mL) at 0 °C for 1.5 h. 3-(trifluoromethoxy)-5-(trifluoromethylsulfanyl)benzoic acid (3.06 g, 10 mmol) was added at 0 °C. The final solution was allowed to reach room temperature. The reaction mixture was stirred at 55° C. for 4 hours and at room temperature overnight. The reaction mixture was diluted with deionized water to a volume of 250 mL. The mixture was cooled to 0 °C causing precipitation of a white solid. The precipitate was filtered, washed successively with water and hexane, and dried in vacuo. Yield 3.2 g (95%).

ESI mass [m/z]: 337.0 [MH] ^-

¹ H NMR (400 MHz, DMSO-d ₆ ): δ = 14.37 (bs, 1H, COOH), 8.48 (s, 1H), 8.46 (s, 1H), 8.42 (s, 1H).

Synthesis of 3-bromo-5-(2,2-dichlorocyclopropyl)benzoic acid (INT-14)

Step 1: 3-Bromo-5-(2,2-dichlorocyclopropyl)benzonitrile

Powdered potassium hydroxide (15 g, 260 mmol) was mixed with 3-bromo-5-vinylbenzonitrile (5.41 g, 26 mmol) and 18-crown-6 (1.03 g, 3.9 mmol) in chloroform (225 mL). The stirred solution was added portion wise at room temperature within 30 minutes. The reaction mixture was stirred at room temperature for 48 hours. The reaction mixture was diluted with dichloromethane to a volume of 400 mL. The solution was washed with water and dried over sodium sulfate. The solvent was removed under reduced pressure to give a dark oil. The oil was purified via flash chromatography (Combiflash) to give 4.55 g (60%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.73 - 7.71 (m, 1H), 7.64 - 7.62 (m, 1H), 7.47 - 7.45 (m, 1H), 2.93 - 2.83 (m, 1H), 2.06 (dd, J = 10.5, 7.7 Hz, 1H), 1.90 - 1.81 (m, 1H). Spectra were recorded on a Varian Gemini 2000.

Step 2: 3-Bromo-5-(2,2-dichlorocyclopropyl)benzoic acid (INT-14)

Thionyl chloride (16.42, mL, 225 mmol) was added to a stirred solution of 3-bromo-5-(2,2-dichlorocyclopropyl)benzonitrile (4.36 g, 15 mmol) in methanol (100 mL) at 0 °C. has been dotted The reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with water to a volume of 300 mL and the final emulsion was extracted with diethyl ether (2Х75 mL). The organic layer was separated, washed with brine and dried over sodium sulfate. The solvent was removed under reduced pressure to give a yellowish oil (4.55 g). The oil was dissolved in isopropanol (35 mL) and the solution was added dropwise to a stirred solution of lithium hydroxide (1.26 g 30 mmol) in deionized water (20 mL) at room temperature and the reaction mixture was stirred for 5 hours. The reaction mixture was diluted with water to a volume of 100 mL. Isopropanol was removed under reduced pressure. The remaining aqueous fraction was washed with diethyl ether (2Х40 mL). A solution of concentrated aqueous HCl in deionized water (20 mL) was then added to the aqueous fraction resulting in the precipitation of a white solid. The precipitate was filtered, washed successively with water and hexane, and dried in a drying oven at 65° C. to give 3.2 g (69%) of the title compound.

ESI mass [m/z]: 311.0 [M+H] ⁺

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ = 13.45 (s, 1H), 7.97 (s, 1H), 7.87 (s, 1H), 7.81 (s, 1H), 3.27 (dd, J = 10.9, 8.5 Hz, 1H), 2.40 - 2.28 (m, 1H), 2.17 - 2.06 (m, 1H). Spectra recorded on Varian Gemini 2000.

Synthesis of 3-bromo-5-(1,1,2,2-tetrafluoroethoxy)benzoic acid (INT-15)

Step 1: Methyl 3-bromo-5-(1,1,2,2-tetrafluoroethoxy)benzoate and methyl 3-bromo-5-(2-bromo-1,1,2,2-tetrafluoro mixture of roethoxy)benzoates

To a solution of 1,2-dibromo-1,1,2,2-tetrafluoroethane (18.0 g, 77.9 mmol, 1.0 eq ) in DMSO (100 mL) was added Cs ₂ CO ₃ (38.1 g, 116 mmol, 1.5 eq ) and methyl 3-bromo-5-hydroxybenzoate (commercially available, 40.4 g, 155 mmol, 2.0 eq ) were added and the mixture was stirred at 60° C. for 12 h. H ₂ O (200 mL) was added to the reaction mixture and extracted with ethyl acetate (150 mL x 3), the organic layer was dried and concentrated to give a mixture of products (22.0 g, 1:1) as a yellow oil.

step 2 : Methyl 3-bromo-5- (1,1,2,2-tetrafluoroethoxy) benzoate

To a solution of the mixture from the previous step (22.0 g, 53.6 mmol, 1.0 eq) in AcOH (100 mL) was added Zn (10.5 g, 161 mmol, 3.0 eq) at 50 °C and the mixture was kept at 50 °C for 12 h. Stir. The reaction mixture was filtered and concentrated under reduced pressure to give a residue. (16.5 g, crude) was obtained as a pale yellow liquid.

Step 3 : 3-bromo-5- (1,1,2,2-tetrafluoroethoxy) benzoic acid (INT-15)

To a solution of methyl 3-bromo-5-(1,1,2,2-tetrafluoroethoxy)benzoate (16.5 g, 49.8 mmol, 1.0 eq) from the previous step in THF (100 mL) was added LiOH. H ₂ O (2.0 M, 49.8 mL, 2.0 eq) was added and the mixture was stirred at 25 °C for 2 h. The reaction was concentrated under reduced pressure to give a residue, diluted with water (50 mL), adjusted to pH = 4 with 2M KHSO ₄ solution and extracted with DCM (30 mL x 2), the combined organic layers were brine ( 50 mL), dried over MgSO ₄ , filtered and concentrated under reduced pressure to give (10.0 g, 31.5 mmol, 63.3) as a white solid.

ESI mass [m/z]: 314.9 [MH] ^-

¹ H-NMR: (400 MHz CDCl ₃ ): δ = 10.69 (br s, 1H), 8.17 (d, J = 1.2 Hz, 1H), 7.89 (s, 1H), 7.64 (s, 1H), 5.78 - 6.12 (m, 1H).

6-(5-{(1S)-1-[3-chloro-5-(1,1,2,2-tetrafluoroethoxy)benzamido]ethyl}-1H-1,2,4-tria Synthesis of sol-1-yl)pyrimidine-4-carboxamide (I-113)

Step 1 : 3-chloro-5- (1,1,2,2-tetrafluoroethoxy) benzoic acid and 3-chloro-5- (1,1,2,2-tetrafluoro-2-iodoethoxy) mixture of benzoic acid

3-Chloro-5-hydroxybenzoic acid (commercially available, 9.3 g, 54 mmol) in 50 mL DMSO, 1-chloro-1,1,2,2-tetrafluoro-2-iodoethane (10.5 g, 40 mmol), potassium carbonate (25 g, 181 mmol) were stirred at 60° C. for 3 days in a thick-walled reaction tube equipped with a pressure-relief valve. The mixture was evaporated under reduced pressure. The residue was aq. It was absorbed in citric acid/ethyl acetate and the aqueous layer was extracted 3 times with ethyl acetate. The combined organic layers were dried over sodium sulfate and evaporated to yield 19.5 g of crude product. Chromatography (silica gel, petrol ether/acetone) was performed in 10.3 g fractions consisting mainly of 3-chloro-5-(1,1,2,2-tetrafluoro-2-iodoethoxy)benzoic acid, and subsequent steps. This yielded an impure fraction containing 3-chloro-5-(1,1,2,2-tetrafluoroethoxy)benzoic acid, which was used directly in

step 2 : 6-(5-{(1S)-1-[3-chloro-5-(1,1,2,2-tetrafluoroethoxy)benzamido]ethyl}-1H-1,2,4- Triazol-1-yl) pyrimidine-4-carboxamide (I-113)

3-Chloro-5-(1,1,2,2-tetrafluoroethoxy)benzoic acid (0.19 g, 0.45 mmol) and HATU (0.34 g, 0.89 mmol) and 6-{5-[(1S)-1 -Aminoethyl] -1H-1,2,4-triazol-1-yl} pyrimidine-4-carboxamide hydrochloride (0.12 g (0.45 mmol) and N, N-diisopropylamine (0.31 ml, 1.78 mmol) was stirred in 1.5 mL DMF each for 1 hour.Solution was combined and stirred at room temperature for 16 hours.Chromatographic purification of the reaction mixture (RP18, water/ACN and 0.1% HCOOH) gave 92 mg (theoretical 42%) was obtained.

See Table 1 for analytical data.

6-(5-{(1S)-1-[3-chloro-5-(1,1,2,2-tetrafluoro-2-iodoethoxy)benzamido]ethyl}-1H-1, Synthesis of 2,4-triazol-1-yl) pyrimidine-4-carboxamide (I-114)

3-chloro-5-(1,1,2,2-tetrafluoro-2-iodoethoxy)benzoic acid (from previous array, 0.18 g, 0.45 mmol) and HATU (0.34 g, 0.89 mmol) and 6- {5-[(1S)-1-aminoethyl]-1H-1,2,4-triazol-1-yl}pyrimidine-4-carboxamide hydrochloride (0.12 g (0.45 mmol) and N,N -Diisopropylamine (0.31 ml, 1.78 mmol) was stirred in 1.5 mL DMF each for 1 hour.Both solutions were combined and stirred at room temperature for 16 hours.Reaction mixture (RP18, water/ACN and 0.1% HCOOH) Chromatographic purification of gave 106 mg (39% of theory).

See Table 1 for analytical data.

Synthesis of 3-(1-fluoro-1-methyl-ethyl)-5-(trifluoromethoxy)benzoic acid (INT-16)

Step 1 : 2-[3-bromo-5-(trifluoromethoxy)phenyl]propan-2-ol

To a solution of 1,3-dibromo-5-(trifluoromethoxy)benzene (20 g, 62.4 mmol) in THF (160 mL) was added i-PrMgCl (1.9 M in THF, 36 mL, 73.2 mmol) under argon. It was instilled at -5°C under The mixture was stirred for 45 min at the same temperature, then acetone (9 g, 156 mmol) was added drop wise. The reaction mixture was stirred for an additional 30 minutes and MTBE (200 mL) was added followed by 10% citric acid (200 mL). The organic layer was separated, washed with brine (3 Х 100 mL), dried and concentrated under reduced pressure. 2-[3-Bromo-5-(trifluoromethoxy)phenyl]propan-2-ol (10.14 g, 33.91 mmol, 54.3 % yield) was obtained after MPLC purification.

step 2 : Methyl 3-(1-hydroxy-1-methyl-ethyl)-5-(trifluoromethoxy)benzoate

To a solution of 2-[3-bromo-5-(trifluoromethoxy)phenyl]propan-2-ol (10.14 g, 33.91 mmol) in MeOH (110 mL), Et ₃ N (6.833 g, 67.82 mmol) and Pd(dppf)Cl ₂ (2.47 g, 3.391 mmol) were added. The mixture was stirred at 130° C. under CO (10 Torr) pressure for 48 hours, diluted with EtOAc (600 mL), filtered through a pad of Celite, then concentrated under reduced pressure. The residue was dissolved in EtOAc (300 mL) and washed with water (2 Х 200 mL). The organic layer was dried over Na ₂ SO ₄ and concentrated under reduced pressure to give methyl 3-(1-hydroxy-1-methyl-ethyl)-5-(trifluoromethoxy)benzoate (8.96 g, 32.21 mmol, 95% yield) provided.

Step 3 : Methyl 3-(1-fluoro-1-methyl-ethyl)-5-(trifluoromethoxy)benzoate

To a solution of methyl 3-(1-hydroxy-1-methyl-ethyl)-5-(trifluoromethoxy)benzoate (8.96 g, 32.21 mmol) in dichloromethane (100 mL) was added Morph-DAST (6.2 g, 35.435 mmol) was added dropwise at -60 °C. The mixture was stirred at room temperature overnight and poured into aqueous sodium bicarbonate. The organic layer was separated, dried over sodium sulfate and concentrated under reduced pressure. Pure methyl 3-(1-fluoro-1-methyl-ethyl)-5-(trifluoromethoxy)benzoate (3.8 g, 13.56 mmol, 42% yield) was obtained after MPLC.

step 4 : 3-(1-fluoro-1-methyl-ethyl)-5-(trifluoromethoxy)benzoic acid (INT-16)

3-(1-fluoro-1-methyl-ethyl)-5-(trifluoromethoxy)benzoate (3.8 g, 13.56 mmol) in a mixture of THF (40 mL)/H ₂ O (12.5 mL) at 0 °C. ), LiOH monohydrate (0.766 g, 18.306 mmol) was added and the mixture was stirred overnight at room temperature. THF was evaporated under reduced pressure, water was acidified to pH=4.5 and extracted with MTBE (2 Х 25 mL). Pure 3-(1-fluoro-1-methyl-ethyl)-5-(trifluoromethoxy)benzoic acid was obtained as a yellow solid after recrystallization from 30% aqueous EtOH (3.17 g, 11.9 mmol, 87,76% yield). has been obtained

ESI mass [m/z neg.]: 265.1 [MH] ⁺

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ = 1.66 (s, 3H), 1.72 (s, 3H), 7.66 (s, 1H), 7.75 (m, 1H), 7.99 (m, 1H) , 13.56 (s, 1H). Spectra were recorded on a Bruker AVANCE III 400 MHz.

of 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride (INT-11) alternative synthesis

Step 1 : tert-butyl N-[(1S)-2-chloro-1-methyl-2-oxo-ethyl]carbamate

Et ₃ N (44.7 g, 442 mmol, 61.6 mL, 0.930 eq) was added. Trimethylacetyl chloride (57.4 g, 476 mmol, 58.5 mL, 1.00 eq) was added dropwise at 0 °C. The reaction mixture was stirred at 20 °C for 16 hours. tert-Butyl N-[(1S)-2-chloro-1-methyl-2-oxo-ethyl]carbamate (98.8 g, crude) in DCM (900 mL) was obtained as a colorless liquid and used in the next step .

step 2 : Ethyl (Z)-N-[(2S)-2-(tert-butoxycarbonylamino)propanoyl]cyclo Propane carboximidate

Et ₃ N (116 g, 1.14 mol, 159 mL, 2.40 eq) was added. Next, ethyl cyclopropanecarboxymidate hydrochloride (71.1 g, 476 mmol, 1.00 eq) was added portionwise at 20°C. After addition, the mixture was stirred at 20 °C for 16 h. Ethyl (Z)-N-[(2S)-2-(tert-butoxycarbonylamino)propanoyl]cyclopropanecarboxymidate (135 g, crude) in DCM was obtained as a colorless liquid and carried on to the next step has been used

Step 3 : tert-butyl N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]carbamate

(6-chloropyrimidin-4-yl)hydrazine (68.7 g, 475 mmol, 1.00 eq) was prepared from ethyl (Z)-N-[(2S)-2-(tert-butoxycarbonyl) in DCM (900 mL) Amino)propanoyl]cyclopropanecarboxymidate (135 g, 475 mmol, 1.00 eq) was added in portions below 20°C. After addition, the mixture was stirred at 20 °C for 16 hours. To the reaction mixture was added H ₂ O (500 mL) and the separated organic layer was washed with brine (200 mL), dried and concentrated. The residue was purified via column chromatography (silica gel, petroleum ether/ethyl acetate = 20/1 to 3/1). tert-butyl N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]carbamate ( 48.0 g, 132 mmol, 27.7% yield over 3 steps) was obtained as a yellow solid.

step 4 : Methyl 6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carb Voxylate (INT-17)

tert-Butyl N-[(1S)-1-[2-(6-chloropyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl in MeOH (1.00 L) To a solution of ]ethyl]carbamate (48.0 g, 132 mmol, 1.00 eq) was added Et ₃ N (26.6 g, 263 mmol, 36.6 mL, 2.00 eq) and Pd(dppf)Cl ₂ (9.63 g, 13.2 mmol, 0.100 eq). ) was added. The suspension was degassed under vacuum and purged with CO several times. The mixture was stirred at 40° C. under CO (50 psi) for 16 hours. The reaction mixture was concentrated. The residue was purified via column chromatography (silica gel, petroleum ether/ethyl acetate = 20/1 to 1/1). Methyl 6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxyl The rate (41.0 g, 106 mmol, 80.2% yield) was obtained as a pale yellow solid.

step 5 : tert-butyl N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]carba Mate (INT-18)

6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxylate (25.0 g, 64.4 mmol, 1.00 eq) was dissolved in THF (150 mL) and MeOH (50 mL). NH ₄ OH (54.1 g, 386 mmol, 59.5 mL, 25% purity, 6.00 eq) was added dropwise at 20 °C. After addition, the mixture was stirred at 20 °C for 5 h. The reaction mixture was concentrated. tert-Butyl N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]carbamate (24.0 g, 60.4 mmol, 93.8% yield, 94% purity) was obtained as a pale yellow solid and used in the next step.

¹ H NMR (400 MHz, CDCl ₃ ): δ 9.08 (d, J = 0.73 Hz, 1 H), 8.65 (s, 1 H), 7.79 (br s, 1 H), 5.96 - 6.07 (m, 1 H) ), 5.81 (br s, 1 H), 5.56 - 5.71 (m, 1 H), 2.02 - 2.12 (m, 1 H), 1.55 (d, J = 6.8 Hz, 3 H), 1.44 (s, 9 H) ), 0.98 - 1.11 (m, 4 H).

Step 6 : 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride (INT-11)

tert-Butyl N-[(1S)-1-[2-(6-carbamoylpyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazole-3- in DCM (20.0 mL) yl]ethyl]carbamate (8.00 g, 21.4 mmol, 1.00 eq ) was added to HCl/dioxane (80.0 mL, 4M). The mixture was stirred at 20 °C for 2 h. The reaction mixture was concentrated. The crude product was triturated with DCM (50.0 mL) at 20 °C for 1 hour and filtered. 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydrochloride (5.54 g, 17.01 mmol, 79.4% yield, 95.1% purity) was obtained as a white solid.

ESI mass [m/z]: 274.2 [amine+H] ⁺

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 9.30 (s, 1H), 8.75 (bs, 2H, NH ₂ ), 8.48 (s, 1H), 8.32 (s, 1H), 8.15 (s, 1H), 5.44 - 5.41 (m, 1H), 2.20 - 2.14 (m, 1H), 1.64 - 1.61 (d, 3H), 1.12 - 1.07 (m, 2H), 1.03 - 0.98 (m, 2H).

6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]-N-methyl-pyrimidine-4-carboxamide hydrochloride ( Synthesis of INT-21)

Step 1 : tert-butyl N-[(1S)-1-[5-cyclopropyl-2-[6-(methylcarbamoyl)pyrimidin-4-yl]-1,2,4-triazol-3-yl] Ethyl]carbamate (INT-19)

Methyl 6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyryl in THF (45.0 mL) To a solution of midine-4-carboxylate (9.00 g, 23.2 mmol, 1.00 eq) was added methanamine (2 M in THF, 34.7 mL, 3.00 eq). The mixture was stirred at 20 °C for 4 hours. After the reaction was complete, the reaction mixture was concentrated. The residue was purified via column chromatography (silica gel, petroleum ether/ethyl acetate = 20/1 to 1/1). tert-Butyl N-[(1S)-1-[5-cyclopropyl-2-[6-(methylcarbamoyl)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl ]Carbamate (8.50 g, 20.8 mmol, 89.9% yield, 95% purity) was obtained as a pale yellow solid.

¹ H NMR (400 MHz, CDCl ₃ ): δ 9.04 (s, 1H), 8.63 (s, 1H), 7.98 (d, 1H), 6.02 - 5.99 (m, 1H), 5.63 (d, 1H), 3.09 (d, 3H), 2.10 - 2.06 (m, 1H), 1.54 (d, 1H), 1.44 (s, 9H), 1.07 - 1.02 (m, 4H).

step 2 : 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]-N-methyl-pyrimidine-4-carboxamide hydrochloride ( INT-21)

Trimethylsilyl chloride (7.07 g, 65.0 mmol, 8.26 mL, 3.00 eq) was added to CF ₃ CH ₂ OH (84.0 mL) and stirred for 30 min. tert-butyl N-[(1S)-1-[5-cyclopropyl-2-[6-(methylcarbamoyl)pyrimidin-4-yl]-1,2 in CF ₃ CH ₂ OH (84.0 mL) 4-triazol-3-yl]ethyl]carbamate (8.40 g, 21.7 mmol, 1.00 eq) was added drop wise to the above solution below 20 °C. After addition, the mixture was stirred at 20 °C for 1 hour. The reaction mixture was concentrated. 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]-N-methyl-pyrimidine-4-carboxamide hydrochloride ( 6.60 g, 19.7 mmol, 91.0% yield, 96.8% purity, HCl) as a pale yellow solid.

¹ H NMR (400 MHz, MeOD): δ 9.19 (d, J = 1.00 Hz, 1 H), 8.52 (d, J = 1.00 Hz, 1 H), 5.59 (q, J = 6.71 Hz, 1 H), 3.25 - 3.38 (m, 2 H), 3.00 (s, 3 H), 2.11 - 2.24 (m, 1 H), 1.75 (d, J = 6.75 Hz, 3 H), 1.01 - 1.16 (m, 4 H) .

6-[5-[(1S)-1-Aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]-N,N-dimethyl-pyrimidine-4-carboxamide hydro Synthesis of Chloride (INT-22)

Step 1 : tert-butyl N-[(1S)-1-[5-cyclopropyl-2-[6-(dimethylcarbamoyl)pyrimidin-4-yl]-1,2,4-triazol-3-yl] Ethyl]carbamate (INT-20)

Methyl 6-[5-[(1S)-1-(tert-butoxycarbonylamino)ethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxyl To a solution of the rate (14.0 g, 36.0 mmol, 1.00 eq) was added a solution of dimethyl amine (2 M in THF, 108 mL, 6.00 eq) THF. The reaction mixture was stirred at 60° C. for 16 hours. The reaction mixture was concentrated. The residue was purified via column chromatography (silica gel, petroleum ether/ethyl acetate = 20/1 to 1/1). tert-Butyl N-[(1S)-1-[5-cyclopropyl-2-[6-(dimethylcarbamoyl)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl ]Carbamate (11.6 g, 27.4 mmol, 76.2% yield, 95% purity) was obtained as a yellow gum.

¹ H NMR (400 MHz, CDCl ₃ ): δ 9.07 (s, 1H), 8.12 (s, 1H), 6.02 - 5.99 (m, 1H), 5.62 (d, 1H), 3.16 (s, 3H), 3.08 (s, 3H), 2.07 - 2.00 (m, 1H), 1.55 (d, 1H), 1.44 (s, 9H), 1.04 - 1.00 (m, 4H).

step 2 : 6-[5-[(1S)-1-Aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]-N,N-dimethyl-pyrimidine-4-carboxamide hydro Chloride (INT-22)

Triemethylsilyl chloride (8.93 g, 82.2 mmol, 10.4 mL, 3.00 eq) was added to CF ₃ CH ₂ OH (110 mL) and stirred for 30 min. tert-butyl N-[(1S)-1-[5-cyclopropyl-2-[6-(dimethylcarbamoyl)pyrimidin-4-yl]-1,2 in CF ₃ CH ₂ OH (84.0 mL); 4-triazol-3-yl]ethyl]carbamate (11.0 g, 27.4 mmol, 1.00 eq) was added drop wise to the above solution below 20 °C. After addition, the mixture was stirred at 20 °C for 1 hour. The reaction mixture was concentrated. 6 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]-N,N-dimethyl-pyrimidine-4-carboxamide Hydrochloride (8.20 g, 23.6 mmol, 86.3% yield, 97.4% purity,) was obtained as a pale yellow solid.

¹ H NMR (400 MHz, MeOD): δ 9.17 (d, J = 1.00 Hz, 1 H), 8.13 (d, J = 1.00 Hz, 1 H), 5.61 (q, J = 6.67 Hz, 1 H), 3.18 (s, 3 H), 3.10 (s, 3 H), 2.11 - 2.24 (m, 1 H), 1.78 (d, J = 6.75 Hz, 3 H), 1.05 - 1.14 (m, 4 H).

Synthesis of 3,5-bis(difluoromethylsulfonyl)benzoic acid (INT-23)

Step 1 : Methyl 3,5-bis(dimethylcarbamothioyloxy)benzoate

Methyl 3,5-dihydroxybenzoate (50 g, 300 mmol) was dissolved in anhydrous DMF (200 mL) under a nitrogen atmosphere. The solution was cooled to 0 °C and DABCO (133 g, 1190 mmol) was added in portions. To the final suspension was added drop wise a solution of N,N-dimethylthiocarbamoyl chloride (147 g, 1190 mmol) in DMF (200 mL) at 0-5°C. When the reaction mixture solidified, more DMF was added to allow efficient stirring. The suspension was allowed to warm to room temperature and stirred for 24 hours. The reaction mixture was poured into water (2000 mL), filtered and the residue was washed with ethanol to give methyl 3,5-bis(dimethylcarbamothioyloxy)benzoate (92 g, 90% yield) as a white crystalline powder and used as is in the next step.

step 2 : Methyl 3,5-bis(dimethylcarbamoylsulfanyl)benzoate

Methyl 3,5-bis(dimethylcarbamothioyloxy)benzoate (8.0 g, 23.3 mmol) was suspended in diphenyl ether (80 mL) and heated to 230-240 °C for 3 h in a sand bath under a nitrogen atmosphere. The reaction mixture was allowed to cool to 30-40 °C, then poured into hexane (160 mL) and allowed to cool slowly to 4 °C. Methyl 3,5-bis(dimethylcarbamoylsulfanyl)benzoate (7.37 g, 92% yield) was obtained as pale beige crystals after filtration and extensive washing with warm hexanes and was used as such in the next step.

step 3 : Methyl 3,5-bis(sulfanyl)benzoate

Under a nitrogen atmosphere, methyl 3,5-bis(dimethylcarbamoylsulfanyl)benzoate (34.2 g, 100 mmol) was added to a mixture of 28% solution of sodium methoxide (43 g, 230 mmol) and methanol (150 mL). Suspended and the reaction mixture was stirred overnight at room temperature. Ice water (500 mL) was added followed by neutralization with concentrated hydrochloric acid. The precipitate was filtered, washed with water and dried under vacuum to give methyl 3,5-bis(sulfanyl)benzoate (12.5 g, 62% yield) as a white powder which was used as such in the next step.

step 4 : Methyl 3,5-bis (difluoromethylsulfanyl) benzoate

To a solution of methyl 3,5-bis(sulfanyl)benzoate (4 g, 20 mmol) in N,N-dimethylformamide (50 mL) was added potassium carbonate (11.4 g, 80 mmol) and sodium chlorodifluoroacetate (11.2 g, 80 mmol) was added. The reaction mixture was heated to 95° C. for 3 hours, diluted with water and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with water and brine, dried over sodium sulfate, filtered and concentrated to give methyl methyl 3,5-bis(difluoromethylsulfanyl)benzoate (3.72 g, 62% yield). Provided as an off-white powder.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.30 (s, 2H), 7.99 (s, 1H), 7.04 - 6.75 (t, 1H), 3.97 (s, 3H). Measured on a Bruker AVANCE III 400 MHz machine.

step 5 : Methyl 3,5-bis (difluoromethylsulfonyl) benzoate

Sodium in a solution of methyl 3,5-bis(difluoromethylsulfanyl)benzoate (3.72 g, 12.5 mmol) in a mixture of carbon tetrachloride (15 mL), acetonitrile (15 mL) and water (35 mL) Periodate (26.4 g, 120 mmol) and trichlororuthenium hydrate (0.1 g, 0.47 mmol) were added. The reaction mixture was stirred at room temperature for 30 min, diluted with water and extracted with dichloromethane. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to give methyl 3,5-bis(difluoromethylsulfonyl)benzoate (2.3 g, 51% yield) as an off-white powder.

¹ H NMR (400 MHz, CDCl ₃ ): δ 9.00 (s, 2H), 8.74 (s, 1H), 6.48 - 6.21 (t, 1H), 4.08 (s, 3H). Measured on a Bruker AVANCE III 400 MHz machine.

step 5 : 3,5-bis(difluoromethylsulfonyl)benzoic acid (INT-23)

Methyl 3,5-bis(difluoromethylsulfonyl)benzoate (2.3 g, 6.3 mmol) was added to a mixture of lithium hydroxide (0.76 g, 12.6 mmol), THF (12 mL) and water (6 mL). added. The reaction was stirred at room temperature for 4 hours, acidified with 1 M hydrochloric acid and the aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure to give 3,5-bis(difluoromethylsulfonyl)benzoic acid (2.03 g, 92% yield) as an off-white powder.

ESI mass [m/z]: 349.0 [MH] ^-

¹ H NMR (400 MHz, DMSO-d6): δ 7.53 (t, 2H), 8.57 (s, 1H), 8.79 (s, 2H), 14.53 (s, 1H). Measured on a Bruker AVANCE III 400 MHz machine.

analysis method

The methods of analysis described below refer to all information in the entire literature, unless the procedure for individual analytical decisions is otherwise explained in individual passages.

mass spectrometry

Determination of [M+H]+ or M- by LC-MS under acid chromatographic conditions was performed using 1 mL formic acid per liter acetonitrile and 0.9 mL formic acid per liter Millipore water as eluent. A column Zorbax Eclipse Plus C18 50 mm * 2.1 mm was used. The temperature of the column oven was 55 °C.

Determination of 1H-NMR data was performed using tetramethylsilane as a reference (0.00 ppm) and using a Bruker Avance III 400 MHz spectrometer equipped with a 1.7 mm TCI probe head, measurements were typically made in solvents CD ₃ CN, CDCl ₃ or from solution in d6-DMSO. Alternatively, a Bruker Avance III 600 MHz instrument equipped with a 5 mm CPNMP probehead or a Bruker Avance NEO 600 MHz instrument equipped with a 5 mm TCI probehead was used for the measurements. Typically, measurements were performed at a probehead temperature of 298 K. Different measured temperatures are clearly displayed.

NMR peak list procedure

1H-NMR data of selected examples are presented in the form of 1H-NMR peak lists. Values in ppm and signal intensities in round brackets are listed for each signal peak. A semicolon is displayed as a separator between value-signal strength pairs.

Therefore, the peak list of examples has the form:

δ ₁ (intensity ₁ );δ ₂ (intensity ₂ );.........;δ _i (intensity _i );......δ _n (intensity _n )

The intensity of the sharp signal correlates with the height of the signal in the printed representation of the 1H-NMR spectrum in cm and shows the actual ratio of the signal intensity. A broad signal or several peaks from the middle of the signal and their relative intensities compared to the most powerful signal in the spectrum can be plotted.

The chemical shift of tetramethylsilane or the solvent in the case where the sample does not contain tetramethylsilane is used to correct the chemical shift for the 1H spectrum. Therefore, tetramethylsilane peaks may, but are not necessarily, present in the 1H-NMR peak list.

The 1H-NMR peak list is equivalent to the classical 1H-NMR print and generally contains all peaks listed in the classical 1H-NMR-interpretation.

In addition, they can, like classic 1 H-NMR prints, show the signal of the peaks of solvents, stereoisomers of any inventive compounds, and/or impurities.

The 1H-NMR solvent signal, tetramethylsilane signal and water signal in the corresponding solvent are excluded from the relative intensity correction as they have very high intensity values.

On average, the peaks of stereoisomers and/or impurities of the compounds according to the present invention generally have a lower intensity (eg purity >90%) compared to the peaks of the compounds according to the present invention.

These stereoisomers and/or impurities may be typical of a particular manufacturing method. Corresponding peaks can therefore help to recognize the reproduction of the manufacturing method via a "by-product-fingerprint".

An expert who calculates peaks of target compounds using known methods (MestreC, with expected values evaluated empirically as well as ACD-simulations) can, if necessary, optionally use additional intensity filters to assign peaks of target compounds. can This assignment will be analogous to normal peak selection in classical 1H-NMR analysis.

The solvents used can be extracted from the JCAMP file using the parameters "Solvent", the spectrometer frequency in "Observation Frequency" and the spectrometer type in "Spectrometer/Data System".

13 C-NMR data are presented as peak listings from broadband separated 13 C-NMR spectra, similar to 1 H-NMR data. 13 C-NMR solvent signals and tetramethylsilane are excluded from the relative intensity correction as these signals can have very high intensities.

Additional details of peak lists and NMR-data descriptions are disclosed in the following publication: "Citation of NMR Peaklist Data within Patent Applications" of the Research Disclosure Database Number 564025.

The compounds according to the invention described in Table 1 below are also preferred compounds of formula (I), wherein R ¹ is hydrogen and X is oxygen and are obtained according to or analogous to the preparation examples described above.

Table 1

Table 2 (intermediates)

biological example

Rhipicephalus (Boophilus) microplus - in vitro contact test on cattle tick larvae (Parkhurst cultivar, resistance to synthetic pyrethroids)

9 mg compound was dissolved in 1 mL acetone and diluted with acetone to the desired concentration. 250 μL of the test solution is filled into a 25 mL glass test tube and evenly distributed on the inner wall by rotation and tilt in a shaker (2 hours, 30 rpm). At a compound concentration of 900 ppm, internal surface of 44.7 cm 2 and uniform distribution, a dose of 5 μg/cm 2 is obtained.

After evaporation of the solvent, each test tube is filled with 20-50 bovine mite larvae ( Rhipicephalus microplus ), sealed with a perforated lid and incubated in an incubator at 85% relative humidity and 27° C. in a horizontal position. do. Efficiency was determined after 48 hours. The larva is tapped on the bottom of the tube and negative gravitational behavior is recorded. Larvae that climb backwards to the top of the vial in a manner similar to untreated control larvae are marked as alive, larvae that do not climb backwards similarly to untreated control larvae, but only move uncoordinatedly or twitch their legs, are marked as moribund and fall to the bottom. Tick larvae that remain and do not move at all are counted as dead.

The compound shows good efficacy against Rhipicephalus microplus at a compound concentration of 5 μg/cm 2 , when an efficacy of at least 80% is monitored. Efficacy of 100% means that all larvae are dead or moribund; 0% means that the larvae are not dead or moribund.

In this test, for example, the following compounds from Preparation Example showed good activity of 100% at an application rate of 5 μg/cm (= 500 g/ha): I-1, I-2, I-3, I -4, I-5, I-6, I-8, I-10, I-18, I-21, I-22, I-28, I-33, I-34, I-35, I-36 , I-37, I-38, I-42, I-46, I-49, I-50, I-51, I-52, I-55, I-56, I-57, I-63, I -64, I-65, I-66, I-67, I-68, I-69, I-73, I-74, I-75, I-76, I-80, I-85, I-87 , I-89, I-95, I-98, I-102, I-135, I-141.

Rhipicephalus (Boophilus) microplus - in-depth examination

Test animal: cattle tick (Rhipicephalus microplus ) Parkhurst breed, SP-resistant

menstruum: dimethyl sulfoxide

To prepare a suitable formulation of active compound, 10 mg of active compound is dissolved in 0.5 mL solvent and the concentrate is diluted with water to the desired concentration.

This compound solution is pipetted into a tube. 8-10 infested, adult, female cattle ticks ( Rhipicephalus microplus ) are placed in a puncture tube. These tubes are immersed in an aqueous compound solution until the mites are completely wetted. After draining the liquid, the mites are transferred to the filter paper in a plastic tray and stored in a climate chamber.

After 7 days, egg turbidity of fertilized eggs is monitored. Eggs that do not show fertility are kept in a climate chamber until hatching after about 42 days. Efficacy of 100% means that all eggs are sterile; 0% means that all eggs are fertilizable.

In this test, for example, the following compound from Preparation Example showed a good activity of 100% at an application rate of 100 ppm: I-1.

Rhipicephalus (Boophilus) microplus - injection test

menstruum: dimethyl sulfoxide

To prepare a suitable formulation of active compound, 10 mg of active compound is dissolved in 0.5 mL solvent and the concentrate is diluted with solvent to the desired concentration.

Five adult engorged female mites ( Rhipicephalus microplus ) are injected with 1 μL compound solution into the abdomen. Ticks are transferred to replication plates and incubated in a climate chamber.

After 7 days, egg turbidity of fertilized eggs is monitored. Eggs that do not show fertility are kept in a climate chamber until hatching after about 42 days. Efficacy of 100% means that all eggs are sterile; 0% means that all eggs are fertilizable.

In this test, for example, the following compounds from preparation examples showed good activity of 100% at an application rate of 4μg/animal: I-1, I-2.

Ctenocephalides felis - oral test

menstruum: dimethyl sulfoxide

To prepare a suitable preparation of active compound, 10 mg of active compound is dissolved in 0.5 mL solvent and the concentrate is diluted with citrated bovine blood to the desired concentration.

Approximately 20 adult non-engorged cat fleas ( Ctenocephalides felis ) are placed in a flea chamber covered with gauze on top and bottom. A chamber sealed at the bottom with parafilm is filled with a blood-compound solution and placed on top of the flea chamber, allowing the fleas to suck blood. The blood chamber is heated to 37° C. while the flea chamber is kept at room temperature.

Mortality (%) is determined after 2 days. 100% means all fleas have been killed; 0% means that the fleas have not been killed.

In this test, for example, the following compounds from Preparation Example showed good activity of 100% at an application rate of 100 ppm: I-1, I-2.

Ctenocephalides felis ( Ctenocephalides felis ) - in vitro contact test adult cat flea

9 mg compound is dissolved in 1 mL acetone and diluted with acetone to the desired concentration. 250 μL of the test solution is filled into a 25 mL glass test tube and evenly distributed on the inner wall by rotation and tilt in a shaker (2 hours, 30 rpm). With a compound concentration of 900 ppm, an internal surface of 44.7 cm 2 and a homogeneous distribution, a dose of 5 μg/cm 2 was obtained.

After evaporation of the solvent, each test tube is filled with 5-10 adult feline fleas ( Ctenocephalides felis ), sealed with a perforated lid and incubated in a supine position at room temperature and relative humidity. Efficacy is determined after 48 hours. The fleas are tapped on the bottom of the tube and incubated on a heating plate at 45-50° C. for up to 5 minutes. Fleas that are immobile or that move incoherently, unable to escape the upward heat, are marked dead or moribund.

The compound shows good efficacy against Ctenocephalides felis when at least 80% efficacy is monitored at a compound concentration of 5 μg/cm 2 . Efficacy of 100% means that all fleas are dead or moribund; 0% means the fleas are not dead or moribund.

In this test, for example, the following compounds from Preparation Example showed good activity of 100% at an application rate of 5 μg/cm 2 (= 500 μg/ha): I-3, I-21, I-33, I -34, I-46, I-49, I-50, I-51, I-52, I-55, I-56, I-57, I-63, I-64, I-65, I-67 , I-68, I-69, I-73, I-74, I-75, I-76, I-80, I-85, I-87, I-89, I-95, I-98, I -102, I-135, I-141.

In this test, for example, the following compounds from Preparation Example showed good activity of 90% at an application rate of 5 μg/cm 2 (= 500 μg/ha): I-5, I-18, I-38, I -42, I-66.

Rhipicephalus sanguineus - in vitro contact test with adult brown dog ticks

9 mg compound is dissolved in 1 mL acetone and diluted with acetone to the desired concentration. 250 μL of the test solution is filled into a 25 mL glass test tube and evenly distributed on the inner wall by rotation and tilt in a shaker (2 hours, 30 rpm). With a compound concentration of 900 ppm, an inner surface of 44.7 cm 2 and a homogeneous distribution, a dose of 5 μg/cm 2 is obtained.

After evaporation of the solvent, each test tube is filled with 5-10 adult dog ticks ( Rhipicephalus sanguineus ), sealed with a perforated lid, and incubated in a supine position at room temperature and relative humidity. Efficacy is determined after 48 hours. The tick is tapped at the bottom of the tube and incubated on a heating plate at 45-50° C. for up to 5 minutes. Ticks that do not move or move incoherently, unable to avoid upward heat, are marked dead or moribund.

When an efficacy of at least 80% is monitored at a compound concentration of 5 μg/cm 2 , the compound shows good efficacy against Rhipicephalus sanguineus . Efficacy of 100% means that all ticks are dead or moribund; 0% means the tick is not dead or moribund.

In this test, for example, the following compounds from Preparation Example showed good activity of 100% at an application rate of 5 μg/cm 2 (= 500 μg/ha): I-1, I-3, I-4, I -5, I-6, I-18, I-21, I-28, I-34, I-42, I-46, I-50, I-51, I-52, I-55, I-56 , I-57, I-63, I-64, I-65, I-67, I-68, I-69, I-73, I-74, I-75, I-76, I-80, I -85, I-87, I-89, I-95, I-98, I-135, I-141.

In this test, for example, the following compounds from Preparation Example showed good activity of at least 80% at an application rate of 5 μg/cm (= 500 μg/ha): I-33, I-36, I-49, I-102.

Diabrotica balteata - spray test

menstruum: 78.0 parts by weight of acetone

1.5 Dimethylformamide in parts by weight

Emulsifier: Alkylarylpolyglycol ethers

To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the specified amount of solvent, and the concentrate is diluted with water containing an emulsifier concentration of 1000 ppm to the desired concentration. Additional test concentrations are prepared by dilution with water containing emulsifier.

Impregnated wheat seeds ( Triticum aestivum ) are placed in multi-well plates filled with agar and partly water and incubated for 1 day to germinate (5 seeds per well). Germinated wheat seeds are sprayed with a test solution containing the active ingredient in the desired concentration. Each unit is then infested with 10-20 larvae of the striped cucumber beetle ( Diabrotica balteata ).

Efficacy (%) is determined after 7 days. 100% means that all seedlings grew like untreated, uninfected controls; 0% means that the seedlings did not grow.

In this test, for example, the following compounds from Preparation Example showed good activity of 100% at an application rate of 100 g/ha (= 32 µg/well): I-3, I-4, I-5, I -6, I-7, I-8, I-10, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20 , I-21, I-22, I-23, I-24, I-25, I-26, I-27, I-28, I-29, I-30, I-31, I-33, I -34, I-35, I-36, I-38, I-39, I-40, I-41, I-42, I-44, I-45, I-46, I-47, I-48 , I-49, I-50, I-51, I-52, I-53, I-54, I-55, I-56, I-58, I-59, I-60, I-63, I -64, I-65, I-66, I-67, I-69, I-71, I-73, I-75, I-76, I-77, I-78, I-79, I-80 , I-81, I-82, I-83, I-84, I-85, I-86, I-87, I-88, I-89, I-90, I-91, I-92, I -93, I-94, I-95, I-98, I-99, I-101, I-102, I-103, I-104, I-105, I-106, I-107, I-109 , I-110, I-112, I-114, I-116, I-117, I-118, I-119, I-120, I-121, I-122, I-124, I-125, I -127, I-128, I-129, I-130, I-131, I-132, I-133, I-134, I-136, I-139, I-140, I-141, I-142 , I-145, I-146, I-148, I-150, I-152, I-153, I-156, I-157, I-158, I-159, I-160, I-161, I -162, I-163, I-165, I-166, I-168, I-169.

In this test, for example, the following compounds from Preparation Example showed good activity of 80% at an application rate of 100 g/ha (= 32 μg/well): I-1, I-2, I-11, I -37, I-43, I-72, I-74, I-115, I-135, I-137, I-138, I-164, I-167.

Meloidogyne incognita - Test

menstruum: 125.0 parts by weight of acetone

To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the specified amount of solvent, and the concentrate is diluted with water to the desired concentration.

The container is filled with sand, active ingredient solution, a suspension containing eggs and larvae of the southern root-knot nematode ( Meloidogyne incognita ) and salad seeds. Germinate salad seeds and grow seedlings. It causes warts in the roots.

After 14 days, the nematicidal activity is determined based on the percentage of gall formation. 100% means that no warts were present, and 0% means that the number of galls present on the roots of the treated plants was the same as that of the untreated control plants.

In this test, for example, the following compound from Preparation Example showed a good activity of 90% at an application rate of 20 ppm: I-21.

Myzus persicae - oral test

menstruum: 100 parts by weight acetone

To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the specified amount of solvent, and the concentrate is diluted with water to the desired concentration.

Fill the microtiter plate with 50 μL compound solution and add 150 μL of IPL41 insect medium (per 33% + 15%) to obtain a total volume of 200 μL per well. The plate is then sealed with parafilm, through which the green peach aphid ( Myzus persicae ) can suck up the compound preparation.

Mortality (%) is determined after 5 days. 100% means that all aphids have been killed and 0% means that no aphids have been killed.

In this test, for example, the following compounds from Preparation Example showed good activity of 100% at an application rate of 4 ppm: I-1, I-2.

Myzus persicae - spray test

menstruum: 78.0 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: Alkylarylpolyglycol ether

To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the specified amount of solvent and diluted with water containing an emulsifier concentration of 1000 ppm to the desired concentration. Additional test concentrations are prepared by dilution with emulsifier containing water.

Chinese cabbage ( Brassica pekinensis ) leaf discs infested with all Aureus green peach aphids ( Myzus persicae ) are sprayed with a preparation of the active ingredient at the desired concentration.

Mortality (%) is determined after 5 days. 100% means that all aphids have been killed, and 0% means that no aphids have been killed.

In this test, for example, the following compounds from Preparation Example showed good activity of 100% at an application rate of 100 g/ha: I-7, I-19, I-20, I-41, I-49, I-55, I-77, I-79, I-80, I-81, I-83, I-85, I-86, I-87, I-88, I-89, I-90, I- 92, I-93, I-94, I-98, I-102, I-112, I-116, I-129, I-133, I-139, I-140, I-142, I-143, I-152, I-160, I-163, I-164, I-166, I-167, I-168.

In this test, for example, the following compounds from Preparation Example showed good activity of 90% at an application rate of 100 g/ha: I-1, I-3, I-5, I-8, I-12, I-18, I-21, I-32, I-34, I-40, I-42, I-45, I-46, I-48, I-50, I-51, I-56, I- 58, I-59, I-60, I-64, I-65, I-66, I-67, I-71, I-72, I-74, I-78, I-82, I-84, I-95, I-97, I-99, I-101, I-103, I-110, I-113, I-115, I-118, I-120, I-121, I-124, I- 134, I-136, I-141, I-150, I-154, I-156, I-159, I-161, I-162, I-169.

In this test, for example, the following compounds from Preparation Example showed a good application rate of 70% at an application rate of 100 g/ha: I-69, I-73, I-125.

Nezara viridula - spray test

menstruum: 78.0 parts by weight of acetone

1.5 Dimethylformamide in parts by weight

Emulsifier: Alkylarylpolyglycol ethers

To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the specified amount of solvent and diluted with water containing 1000 ppm of an emulsifier to the desired concentration. Additional test concentrations are prepared by dilution with emulsifier containing water.

Barley plants ( Hordeum vulgare ) are sprayed with a test solution containing the desired concentration of the active ingredient and infested with larvae of the southern green stink bug ( Nezara viridula ).

After 4 days, mortality (%) is determined. 100% means that all stink bugs have been killed; 0% means that the stink bug has not been killed.

In this test, for example, the following compounds from Preparation Example showed good activity of 100% at an application rate of 500 g/ha: I-7, I-12, I-18, I-19, I-21, I-22, I-23, I-25, I-30, I-31, I-32, I-33, I-34, I-38, I-42, I-44, I-45, I- 46, I-48, I-49, I-51, I-58, I-59, I-60, I-61, I-62, I-64, I-65, I-66, I-67, I-69, I-72, I-73, I-74, I-75, I-76, I-77, I-78, I-79, I-80, I-81, I-82, I- 83, I-84, I-85, I-86, I-87, I-88, I-89, I-90, I-92, I-93, I-94, I-95, I-96, I-98, I-99, I-101, I-102, I-110, I-116, I-117, I-118, I-119, I-120, I-121, I-122, I- 124, I-125, I-126, I-127, I-128, I-129, I-130, I-131, I-132, I-135, I-136, I-138, I-139, I-140, I-141, I-142, I-143, I-147, I-148, I-150, I-154, I-155, I-162.

In this test, for example, the following compounds from Preparation Example showed good activity of 90% at an application rate of 500 g/ha: I-3, I-28, I-41, I-70, I-71.

In this test, for example, the following compounds from Preparation Example showed good activity of 100% at an application rate of 100 g/ha: I-21, I-34, I-44, I-49, I-51, I-116, I-118, I-120, I-121, I-124, I-125, I-126, I-128, I-135.

In this test, for example, the following compounds from Preparation Example showed good activity of 90% at an application rate of 100 g/ha: I-3, I-7, I-19, I-32, I-42, I-127.

Nilaparvata lugens - spray test

menstruum: 78.0 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: Alkylarylpolyglycol ethers

To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the specified amount of solvent and diluted with water, up to the desired concentration, containing an emulsifier concentration of 1000 ppm. Additional test concentrations are prepared by dilution with emulsifier containing water.

Rice plants ( Oryza sativa ) are sprayed with the preparation of the active ingredient at the desired concentration, and the plants are infected with brown planthopper ( Nilaparvata lugens ).

Mortality (%) is determined after 4 days. 100% means that all myrtle have been killed, and 0% means that no myrtle has been killed.

In this test, for example, the following compounds from Preparation Example showed good activity of 100% at an application rate of 500 g/ha: I-8, I-23, I-29, I-31, I-33, I-38, I-39, I-44, I-49, I-50, I-51, I-57, I-59, I-60, I-63, I-64, I-67, I- 72, I-73, I-74, I-75, I-76, I-77, I-78, I-79, I-80, I-81, I-82, I-83, I-92, I-93, I-94, I-101, I-116, I-118, I-120, I-121, I-122, I-125, I-126, I-128, I-129, I- 130, I-133, I-134, I-135, I-136, I-139, I-141, I-142, I-154.

In this test, for example, the following compounds from Preparation Example showed good activity of 90% at an application rate of 500 g/ha: I-7, I-32, I-61, I-85, I-90, I-102, I-115, I-140.

Spodoptera frugiperda - spray test

menstruum: 78.0 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: Alkylarylpolyglycol ethers

To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the specified amount of solvent and diluted with water, up to the desired concentration, containing an emulsifier concentration of 1000 ppm. Additional test concentrations are prepared by dilution with emulsifier containing water.

Corn ( Zea mays ) leaf parts are sprayed with a preparation of the active ingredient in the desired concentration. When dry, the leaf sectors are infested with autumn armyworm ( Spodoptera frugiperda ) larvae.

Mortality (%) is determined after 7 days. 100% means that all larvae have been killed, and 0% means that no larvae have been killed.

In this test, for example, the following compounds from Preparation Example showed good activity of 100% at an application rate of 100 g/ha: I-1, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-15, I-16, I-18, I-19, I-20, I- 21, I-22, I-24, I-25, I-26, I-27, I-28, I-29, I-30, I-31, I-32, I-33, I-34, I-35, I-36, I-38, I-39, I-40, I-41, I-42, I-43, I-45, I-46, I-47, I-48, I- 49, I-50, I-51, I-52, I-54, I-55, I-56, I-57, I-58, I-63, I-64, I-65, I-66, I-67, I-68, I-69, I-70, I-71, I-72, I-73, I-74, I-75, I-76, I-78, I-79, I- 80, I-81, I-82, I-83, I-84, I-85, I-86, I-87, I-88, I-89, I-90, I-91, I-92, I-93, I-94, I-95, I-97, I-98, I-99, I-101, I-102, I-103, I-104, I-105, I-106, I- 107, I-108, I-109, I-110, I-111, I-112, I-113, I-114, I-115, I-116, I-117, I-118, I-119, I-120, I-121, I-122, I-123, I-124, I-125, I-127, I-129, I-130, I-132, I-133, I-134, I- 135, I-136, I-137, I-138, I-140, I-141, I-142, I-143, I-144, I-145, I-146, I-147, I-148, I-150, I-152, I-153, I-154, I-155, I-156, I-157, I-158, I-159, I-161, I-162, I-163, I- 165, I-166, I-167, I-168, I-169.

In this test, for example, the following compounds from Preparation Example showed good activity of 83% at an application rate of 100 g/ha: I-62, I-100, I-151, I-160.

Aedes aegypti test (AEDSAE surface treatment and contact assay)

menstruum: Acetone + 2000 ppm Rapeseed Oil Methyl Ester (RME)

To prepare a sufficient, active ingredient-containing solution, it is necessary to dissolve the test compound in a solvent-mix (2 mg/mL of acetone/RME 2000 ppm). This solution is pipetted onto a glazed tile and, after evaporation of acetone, adult mosquitoes of the species MONHEIM, Aedes aegypti, are placed on a dry surface. Exposure time is 30 minutes. Mortality (%) is determined 24 hours after contact of the insect with the treated surface. 100% mortality means that all test insects have been killed, 0% means that no insects have been killed.

The following examples show efficacy of 80-100% at a surface concentration of 20 mg/m 2 in this test: I-1, I-2, I-3, I-4, I-5, I-7, I- 8, I-10, I-19, I-20, I-21, I-25, I-33, I-34, I-36, I-40, I-42, I-49, I-51, I-73, I-74, I-86, I-90, I-93, I-102.

The following examples show efficacy of 80-100% at a surface concentration of 4 mg/m in this test: I-1, I-2, I-8, I-10, I-19, I-20, I- 21, I-25, I-33, I-34, I-41, I-42, I-49, I-51, I-73, I-74, I-86, I-90, I-93, I-102.

Culex quinquefasciatus test (CULXFA surface treatment and contact assay)

Solvent: Acetone + 2000 ppm Rapeseed Oil Methyl Ester (RME)

To prepare a sufficient, active ingredient-containing solution, it is necessary to dissolve the test compound in a solvent-mix (2 mg/mL acetone/RME 2 000 ppm). This solution is pipetted onto a glazed tile and, after acetone evaporation, adult mosquitoes of the species P00, Culex quinquefasciatus, are placed on a dry surface. Exposure time is 30 minutes. Mortality (%) is determined 24 hours after exposure of insects to the treated surface. 100% mortality means that all tested insects have been killed, while 0% means that no insects have been killed.

The following examples showed 80-100% efficacy at a surface concentration of 20 mg/m in this test: I-20, I-33, I-49, I-51, I-73, I-74, I- 90, I-93, I-102.

The following examples showed 80-100% efficacy at a surface concentration of 4 mg/m in this test: I-21, I-33, I-42, I-49, I-51, I-73, I- 74, I-90, I-93, I-102.

Musca domestica test (MUSCDO Surface Treatment and Contact Assay)

menstruum: Acetone + 2000 ppm Rapeseed Oil Methyl Ester (RME)

It is necessary to dissolve the test compound in a solvent-mix (2 mg/mL acetone/RME 2000 ppm) to prepare a sufficient, active ingredient-containing solution. This solution is pipetted onto a glazed tile and, after evaporation of acetone, adult flies of the species WHO-N, Musca domestica , are placed on the dried surface. Exposure time is 30 minutes. Mortality (%) is determined 24 hours after contact of the insect with the treated surface. 100% mortality means that all insects have been killed, while 0% means that no insects have been killed.

The following examples showed 80-100% efficacy at a surface concentration of 20 mg/m in this test: I-1, I-10, I-20, I-21, I-33, I-36, I- 39, I-42, I-49, I-51, I-73, I-74, I-8, I-86, I-90, I-93, I-102.

The following examples show efficacy of 80-100% at a surface concentration of 4 mg/m in this test: I-21, I-33, I-36, I-39, I-42, I-49, I- 51, I-73, I-74, I-90, I-93, I-102.

Blattella germanica test (BLTTGE surface treatment and contact assay)

menstruum: Acetone + 2000 ppm Rapeseed Oil Methyl Ester (RME)

It is necessary to dissolve the test compound in a solvent-mix (2 mg/mL acetone/RME 2000 ppm) to prepare a sufficient, active ingredient-containing solution. This solution is pipetted onto a glazed tile and, after evaporation of acetone, adult animals of the species Blattella germanica , of the species PAULINIA, are placed on the dried surface. Exposure time is 30 minutes.

Mortality (%) is determined 24 hours after contact of the insect with the treated surface. 100% mortality means that all tested insects have been killed, while 0% means that no insects have been killed.

The following examples show 80-100% efficacy at a surface concentration of 20 mg/m in this test: II-21, I-49, I-51, I-73, I-74, I-90, I- 93, I-102.

The following examples showed efficacy of 80-100% at a surface concentration of 4 mg/m in this test: I-21, I-49, I-51, I-73, I-74, I-93, I- 102.

comparative example

Spodoptera frugiperda - spray test (SPODFR)

menstruum: 78.0 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: Alkylarylpolyglycol ether

To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the specified amount of solvent and diluted with water, up to the desired concentration, containing an emulsifier concentration of 1000 ppm. Additional test concentrations are prepared by dilution with emulsifier containing water.

Corn ( Zea mays ) leaf parts are sprayed with a preparation of the active ingredient in the desired concentration. When dried, the leaf parts become infected with fall armyworm larvae ( Spodoptera frugiperda ).

After the specified time period, mortality (%) is determined. 100% means that all larvae have been killed, and 0% means that no larvae have been killed.

In this test, for example, the following compounds from preparations show superior levels of activity compared to the prior art: see Tables 3 and 4.

Myzus persicae - oral test (MYZUPE oral)

Solvent: 100 parts by weight of acetone

To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the specified amount of solvent, and the concentrate is diluted with water to the desired concentration.

Fill a microtiter plate with 50 μL of compound solution and add 150 μL of IPL41 insect medium (per 33% + 15%) to obtain a total volume of 200 μL per well. The plate is then sealed with parafilm through which a mixed population of green peach aphids ( Myzus persicae ) can absorb the compound preparation.

After 5 days, mortality (%) is determined. 100% means that all aphids have been killed, and 0% means that no aphids have been killed.

In this test, for example, the following compounds from preparations show a superior level of activity compared to the prior art: see Table 3.

Myzus persicae - spray test (MYZUPE)

menstruum: 78.0 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: Alkylarylpolyglycol ether

To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the specified amount of solvent and diluted with water, up to the desired concentration, containing an emulsifier concentration of 1000 ppm. Additional test concentrations are prepared by dilution with emulsifier containing water.

All aura green peach aphids (Mijuus persicae ( Myzus persicae ) infected Chinese cabbage ( Brassica pekinensis ) leaf discs are sprayed with a preparation of the active ingredient at the desired concentration.

After all specified time periods, mortality (%) is determined. 100% means that all aphids have been killed, and 0% means that no aphids have been killed.

In this test, for example, the following compounds from preparations show a superior level of activity compared to the prior art: see Table 4.

Table 3 - Comparative Example (I)

Table 4 - Comparative Example (II)

Claims (19)

A compound of formula (I)

[In the expression,
X is O or S;
R ¹ is hydrogen;
R ² is selected from the substructures Q1 and Q2 below, wherein the bond with the C=X-group is represented by #:

in the expression,
R ²¹ is halogen, -CN, -SF ₅ , C ₁ -C ₃ haloalkyl, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ haloalkylthio, C ₁ -C ₃ haloalkylsulfinyl, C ₁ - C ₃ haloalkylsulfonyl, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylsulfinyl, C ₁ -C ₃ alkylsulfonyl, C ₃ -C ₄ cycloalkylthio, C ₃ -C ₄ cycloalkyl group phenyl, C ₃ -C ₄ cycloalkylsulfonyl, phenylsulfonyl, wherein phenyl is 1 to 2 substituent(s) selected from the group of halogen, -CN, methyl, trifluoromethyl or trifluoromethoxy optionally substituted with); or cyclopropyl, wherein cyclopropyl is optionally substituted with 1 to 2 substituent(s) selected from the group of halogen, -CN, methyl or trifluoromethyl;
R ²² is hydrogen, halogen, -CN, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ haloalkoxy or C ₁ -C ₃ haloalkylsulfonyl;
R ³ is -CN or a substituent selected from substructure S1 below, wherein the bond to the pyrimidine is represented by #:

R ³¹ is hydrogen or C ₁ -C ₃ alkyl;
R ³² is hydrogen, C ₃ -C ₆ cycloalkyl or C ₁ -C ₃ alkyl, wherein C ₃ -C ₆ cycloalkyl and C ₁ -C ₃ alkyl are halogen, -CN, C ₃ -C ₆ cycloalkyl and optionally substituted with 1 to 3 substituents selected from the group of C ₁ -C ₃ alkoxy;
R ⁴ is hydrogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or C ₃ -C ₄ cycloalkyl; According to claim 1,
X is O or S;
R ¹ is hydrogen;
R ² is selected from substructures Q1 and Q2 below, wherein the bond with the C=X-group is indicated by #;

in the expression,
R ²¹ is fluorine, chlorine, bromine, iodine, -CN, cyclopropyl, 1-cyanocyclopropyl, 2,2-dichlorocyclopropyl, difluoromethyl, 1,1-difluoroethyl, trifluoromethyl , chlorodifluoromethyl, 2-fluoropropan-2-yl, difluoromethoxy, trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetra Fluoro-2-iodoethoxy difluoromethylthio, trifluoromethylthio, 1,1,2,2-tetrafluoroethylthio difluoromethylsulfonyl, trifluoromethylsulfonyl, 1, 1,2,2-tetrafluoroethylsulfonyl, methylsulfanyl, methylsulfinyl, methylsulfonyl, ethylsulfonyl, cyclopropylsulfonyl or 4-chlorophenyl-sulfonyl;
R ²² is hydrogen, fluorine, chlorine, bromine, iodine, -CN, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylsulfonyl, trifluoromethylsulfonyl; ;
R ³ is -CN or a substituent selected from substructure S1 below, wherein the bond to the pyrimidine is represented by #;

in the expression,
R ³¹ is hydrogen or methyl;
R ³² is hydrogen, cyclopropyl or C ₁ -C ₃ alkyl, wherein C ₁ -C ₃ alkyl is optionally substituted with 1 to 3 substituents selected from the group of fluorine, chlorine, -CN, cyclopropyl and methoxy being);
R ⁴ is hydrogen, methyl or cyclopropyl. According to claim 1 or 2,
X is O;
R ¹ is hydrogen;
R ² is (3,5-dibromophenyl), (3,5-dichlorophenyl), (3-chloro-5-methylsulfonylphenyl), 3-bromo-5-methylsulfonylphenyl, (3 -Cyano-5-fluorophenyl), 3-chloro-5-cyanophenyl, 3-bromo-5-cyanophenyl, 3,5-dicyanophenyl, 3-(1,1,2,2 -Tetrafluoroethylthio)phenyl, 3-(1-cyanocyclopropyl)-5-(trifluoromethoxy)phenyl, 3-(difluoromethoxy)-5-fluorophenyl, 3-(difluoro) Lomethoxy)-5-iodophenyl, 3-(difluoromethylsulfonyl)-5-(trifluoromethoxy)phenyl, 3-(trifluoromethoxy)-5-(trifluoromethylsulfonyl) Phenyl, 3-(trifluoromethoxy)phenyl, 3-(trifluoromethyl)phenyl, 3-(trifluoromethylsulfonyl)phenyl, 3,5-bis(difluoromethoxy)phenyl, 3-( 2-fluoropropan-2-yl) -5- (trifluoromethoxy) phenyl, 3,5-bis (trifluoromethoxy) phenyl, 3,5-bis (difluoromethyl) phenyl, 3,5 -bis(trifluoromethyl)phenyl, 3-(difluoromethoxy)-5-(trifluoromethoxy)phenyl, 3,5-bis(difluoromethylsulfonyl)phenyl, 3,5-bis( Trifluoromethylsulfonyl) phenyl, 3-bromo-5- (1,1,2,2-tetrafluoroethoxy) phenyl, 3-bromo-5- (2,2-dichlorocyclopropyl) phenyl , 3-bromo-5- (difluoromethoxy) phenyl, 3-bromo-5- (trifluoromethoxy) phenyl, 3-chloro-5- (1,1,2,2-tetrafluoro- 2-iodoethoxy)phenyl, 3-chloro-5-(1,1,2,2-tetrafluoroethoxy)phenyl, 3-chloro-5-(4-chlorophenyl)sulfonylphenyl, 3- Chloro-5- (difluoromethylsulfonyl) phenyl, 3-chloro-5- (trifluoromethoxy) phenyl, 3-chloro-5- (trifluoromethyl) phenyl, 3-chloro-5- (1 , 1-difluoroethyl) phenyl, 3-chloro-5- (chlorodifluoromethyl) phenyl, 3-chloro-5- (trifluoromethylsulfonyl) phenyl, 3-bromo-5- (tri Fluoromethylsulfonyl) phenyl, 3-chloro-5- (trifluoromethylthio) phenyl, 3-cyano-5- (trifluoromethoxy) phenyl, 3-cyclopropyl-5- (difluoromethoxy )phenyl, 3-cyclopropyl-5-(trifluoro lomethoxy) phenyl, 3-cyclopropylsulfonyl-5- (trifluoromethoxy) phenyl, 3-fluoro-5- (trifluoromethoxy) phenyl, 3-methylsulfonylphenyl, 3- (difluoromethyl Toxy) -5-methylsulfanylphenyl, 3- (difluoromethoxy) -5-methylsulfonylphenyl, 3-methylsulfonyl-5- (trifluoromethoxy) phenyl, 3-methylsulfonyl-5- (Trifluoromethyl)phenyl, 2,6-dibromopyridin-4-yl, 2-(trifluoromethoxy)pyridin-4-yl, 2-chloro-6-(trifluoromethoxy)pyridin-4 -yl, 2-bromo-6-methylsulfonyl-pyridin-4-yl or 2-chloro-6-(1-cyanocyclopropyl)pyridin-4-yl;
R ³ is -CN, aminocarbonyl, methylcarbamoyl, ethylcarbamoyl, (isopropylamino)carbonyl, (difluoroethylamino)carbonyl, (3,3,3-trifluoropropylamino)carbonyl; carbonyl, (cyclopropylamino)carbonyl, dimethylaminocarbonyl, [ethyl(methyl)amino]carbonyl, [isopropyl(methyl)amino]carbonyl or [cyclopropylmethyl(methyl)amino]carbonyl;
R ⁴ is hydrogen, methyl or cyclopropyl;
R ⁴ is hydrogen, methyl or cyclopropyl. 4. A compound according to any one of claims 1 to 3, characterized in that it has a structure according to formula (I'):

(Wherein the structural components R ¹ , R ² , R ³ and R ⁴ have the meanings given in claim 1 or given in claim 2 or in claim 3). 4. A compound according to any one of claims 1 to 3, characterized in that it has a structure according to formula (I"), wherein R ¹ is hydrogen:

(Wherein the structural components R ² , R ³ and R ⁴ have the meanings given in claim 1, or the meanings given in claim 2 or 3). 4. A compound according to any one of claims 1 to 3, characterized in that it has a structure according to formula (I"'), wherein R ¹ is hydrogen:

(Wherein the structural components R ² , R ³ and R ⁴ have the meanings given in claim 1 or given in claim 2 or in claim 3). A compound of formula ( a ):

(Wherein, R ¹ and R ⁴ have the meanings provided in claim 1 or 2 or 3). Compound 6-[5-(1-aminoethyl)-1H-1,2,4-triazol-1-yl]pyrimidine-4-carbonitrile hydrochloride, tert-butyl {1-[1-(6- Cyanopyrimidin-4-yl)-1H-1,2,4-triazol-5-yl]ethyl}carbamate, tert-butyl N-[(1S)-1-[2-(6-cyano Pyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]carbamate, 6-[5-[(1S)-1-aminoethyl]-1,2,4-triazole -1-yl]pyrimidine-4-carbonitrile;2,2,2-trifluoroacetic acid, tert-butyl N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl )-5-methyl-1,2,4-triazol-3-yl]ethyl]carbamate, 6-[5-[(1S)-1-aminoethyl]-3-methyl-1,2,4- Triazol-1-yl] pyrimidine-4-carbonitrile hydrochloride, tert-butyl N-[(1S)-1-[2-(6-cyanopyrimidin-4-yl)-5-cyclopropyl- 1,2,4-triazol-3-yl]ethyl]-carbamate, 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazole-1 -yl]pyrimidine-4-carbonitrile hydrochloride, 6-[5-[(1S)-1-aminoethyl]-3-methyl-1,2,4-triazol-1-yl]pyrimidine-4 -Carboxamide hydrochloride, 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxamide hydro Chloride, 2-chloro-6-(1-cyanocyclopropyl)pyridine-4-carboxylic acid, 6-[5-[(1S)-1-aminoethyl]-1,2,4-triazole-1 -yl]pyrimidine-4-carboxamide hydrochloride, 3-(trifluoromethoxy)-5-(trifluoromethylsulfonyl)benzoic acid, 3-bromo-5-(2,2-dichlorocyclopropyl )benzoic acid, and 3-bromo-5-(1,1,2,2-tetrafluoroethoxy)benzoic acid, methyl 6-[5-[(1S)-1-(tert-butoxycarbonylamino) Ethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyrimidine-4-carboxylate, tert-butyl N-[(1S)-1-[2-(6-carbamoyl Pyrimidin-4-yl)-5-cyclopropyl-1,2,4-triazol-3-yl]ethyl]carbamate, tert-butyl N -[(1S)-1-[5-cyclopropyl-2-[6-(methylcarbamoyl)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl]carbamate; tert-Butyl N-[(1S)-1-[5-cyclopropyl-2-[6-(dimethylcarbamoyl)pyrimidin-4-yl]-1,2,4-triazol-3-yl]ethyl ]Carbamate, 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]-N-methyl-pyrimidine-4-carboxa Mid hydrochloride, 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]-N,N-dimethyl-pyrimidine-4- In the case of carboxamide hydrochloride, 3-(1-fluoro-1-methyl-ethyl)-5-(trifluoromethoxy)benzoic acid, 3,5-bis(difluoromethylsulfonyl)benzoic acid, amine also free amines in the case of their salts and amine hydrochlorides. A formulation, in particular a chemical fertilizer formulation, comprising at least one compound of formula (I) according to any one of claims 1 to 6. 10. The formulation according to claim 9, further comprising at least one bulking agent and/or at least one surface-active substance. 11. Preparation according to claim 9 or 10, characterized in that the compound of formula (I) is present in admixture with at least one further active compound. A method for controlling pests, in particular pests, wherein a compound of formula (I) according to any one of claims 1 to 6 or a formulation according to any one of claims 9 to 11 is used. And / or characterized in that it is allowed to act on their habitat, control method. The method of claim 12, wherein the pest is a pest, and includes an insect, arachnid or nematode, or the pest is an insect, arachnid or nematode, characterized in that, the control method. Use of a compound of formula (I) according to any one of claims 1 to 6 or a formulation according to any one of claims 9 to 11 for controlling pests. 15. Use according to claim 14, characterized in that pests include insects, arachnids or nematodes, or pests are insects, arachnids or nematodes. 16. The use according to claim 14 or 15, which is crop protection. Use according to claim 14 or 15 in the field of animal health. A method for protecting seeds or germinating plants from pests, in particular pests, comprising treating the seeds with a compound of formula (I) according to any one of claims 1 to 6 or any one of claims 9 to 11. A method of protection comprising the step of contacting an agent according to any one of claims. Seed obtained by the method according to claim 18.